CN107511172A - Beta molecular sieve catalysts, preparation method and application - Google Patents
Beta molecular sieve catalysts, preparation method and application Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—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
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—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
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
- C07C2/64—Addition to a carbon atom of a six-membered aromatic ring
- C07C2/66—Catalytic processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
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Abstract
The present invention relates to a kind of Beta molecular sieve catalysts, preparation method and application.The Beta molecular sieve catalysts, in terms of parts by weight, including following component：A) 92~99 parts of Beta molecular sieves；B) 1~8 part of sial glue caking agent；The step of sial glue caking agent is contacted by silicon source, silicon source and alkali obtains.
Description
Technical field
The present invention relates to a kind of Beta molecular sieve catalysts, preparation method and application.
Background technology
Beta molecular sieves were successfully synthesized first by Mobil companies in 1967.It has unique three-dimensional twelve-ring hole
Road system, a linear channels, 0.76 nanometer × 0.64 nanometer of aperture, a bending duct, aperture 0.55 nanometer × 0.55 is received
Rice.The estimation structure of Beta molecular sieves is extremely complex, includes a variety of crystal formations, and such as A types (* BEA structures), Type B and c-type, (BEC is tied
Structure).Beta molecular sieves are widely used due to its stronger acidity and unique pore passage structure in petroleum chemical industry.As made
It is used for the separation of aromatic hydrocarbon for adsorbent, gasoline upgrading, hydroisomerizing is used for as catalyst, is hydrocracked, catalytic reforming takes off
In the courses of reaction such as wax, the alkylation of benzene, transalkylation.Succeed by catalyst made from active component of Beta molecular sieves
Applied to benzene and preparing ethylbenzene by liquid phase alkylation of ethylene technique and benzene and propylene liquid-phase alkylation preparing isopropylbenzene (cumene) technique.
Especially, in order to meet the requirement of commercial Application, molecular sieve and the additives such as binding agent, pore creating material need to be mixed into
Type, the catalyst with certain size, shape and intensity is made.But the addition of binding agent can more cover the activity of molecular sieve
Center, at the same can in limiting catalyst as active component molecular sieve content, the content of general molecular sieve is less than 80 matter
Measure %.Therefore, before the quantity in the activated centre in the Beta molecular sieve catalysts of the shaping of commercialization is far below shaping
Beta molecular sieves.
In order to overcome the problem of containing binding agent, activated centre in catalyst less, document CN105439164A discloses one
The preparation method of kind binder free Beta molecular sieve catalysts, Beta molecular sieves are converted into by secondary turn of crystalline substance by binding agent.So
And this method turns brilliant required time length (48~120 hours), and then cause catalyst strength to reduce, commercial Application can not be met
Requirement；Meanwhile 5 mass % binding agent is still remained in the catalyst of gained.
In addition, the present inventor influences notable by largely testing discovery, catalyst strength on catalytic performance.
Benzene and olefin liquid phase are alkylated in the reaction of alkylbenzene processed, and the compression strength of catalyst is not the higher the better, it is necessary to find conjunction
Suitable compression strength just can guarantee that the catalytic performance of catalyst.
The content of the invention
The technical problems to be solved by the invention are that prior art uses Ludox, aluminum oxide bonding to be present for binding agent
Catalyst strength is too high when agent dosage is big, molecular sieve content is low, catalytic activity is low, and consumption of binder hour catalyst strength is low,
Efflorescence is serious；And the problem of long the time required to secondary crystallization.The present invention provides a kind of new Beta molecular sieve catalysts.The catalysis
Agent is realized the shaping of molecular sieve using very small amount of binding agent can, molecule has directly been made using Alusil as binding agent
The Beta molecular sieve catalysts that content is not less than 95% are sieved, are that can obtain the catalyst that intensity is high, activity is good without secondary crystallization,
Meet benzene and ethene and benzene and requirement of the propylene liquid-phase alkylation reaction to catalyst, be adapted to large-scale industrial production.
In order to solve the above technical problems, the technical scheme that the present invention takes is as follows：A kind of Beta molecular sieve catalysts, with weight
Measure number meter, including following component：
A) 92~99 parts of Beta molecular sieves；
B) 1~8 part of sial glue caking agent；
The step of sial glue caking agent is contacted by silicon source, silicon source and alkali obtains；Silicon source is with SiO2Meter, silicon source
With Al2O3Meter, alkali silicon mol ratio alkali/SiO2=0~0.3, silica alumina ratio SiO2/Al2O3=25~85.
In above-mentioned technical proposal, the preferred alkali/SiO of alkali silicon mol ratio2=0.02~0.3, more preferably alkali/SiO2=0.03~
0.22, more preferably alkali/SiO2=0.04~0.18, most preferably alkali/SiO2=0.06~0.12.
In above-mentioned technical proposal, the preferred SiO of silica alumina ratio2/Al2O3=25~60, more preferably SiO2/Al2O3=30~
50。
In above-mentioned technical proposal, the silicon source is Y selected from Ludox, smoke silica gel, waterglass or formula4-nSiXnContain
At least one of silicon compound；Formula Y4-nSiXnIn, n is 1~4 integer, and Y is alkenyl group, preferably methyl, ethyl
Or propyl group；X is selected from Cl, methoxyl group OMe, ethyoxyl OEt or trimethylsiloxy group OSiMe3.Silicon source is preferably Ludox, smoke
At least one of silica gel.
In above-mentioned technical proposal, source of aluminium is in sodium aluminate, aluminium hydroxide, aluminum sulfate, aluminum nitrate or aluminium chloride
It is at least one.
In above-mentioned technical proposal, the alkali is selected from quaternary ammonium base, using alkali metal or alkali earth metal as cation
At least one of alkali；The quaternary ammonium base is selected from TMAH, tetraethyl ammonium hydroxide, TPAOH, four
Butyl ammonium hydroxide, N, N, N- front three adamantyl ammonium hydroxide or dimethyl diethyl ammonium hydroxide.Alkali is preferably NaOH
Or at least one of KOH.
In above-mentioned technical proposal, in terms of parts by weight, the content of Beta molecular sieves is preferably 95~99 parts, more preferably 96
~99 parts；The content of sial glue caking agent is preferably 1~5 part, more preferably 1~4 part.
In above-mentioned technical proposal, the crystal grain diameter of the Beta molecular sieves is 10~200 nanometers, the sial of Beta molecular sieves
Mol ratio SiO2/Al2O3=15~80.
In above-mentioned technical proposal, the compression strength of the Beta molecular sieve catalysts for 60~120 newton/centimetre, preferably
For 65~100 newton/centimetre, more preferably 65~90 newton/centimetre.
In above-mentioned technical proposal, in terms of parts by weight, the catalyst includes 0~0.5 part of phosphorus.
In above-mentioned technical proposal, in terms of parts by weight, the catalyst includes 0~0.5 part of thulium.
In above-mentioned technical proposal, the thulium is selected from least one of yttrium, lanthanum, cerium or neodymium.
The content of each component is on the basis of the Beta molecular sieves after roasting in Beta molecular sieves of the present invention.
The present invention also provides a kind of preparation method of Beta molecular sieve catalysts.It the described method comprises the following steps：
A) synthesis state Beta molecular sieves are provided；
B) synthesis state Beta molecular sieves, silicon source, silicon source and the alkali straight forming obtain the Beta molecular sieve catalysts；
Wherein, the silicon source is Y selected from Ludox, smoke silica gel, waterglass or formula4-nSiXnSilicon-containing compound in
At least one；Formula Y4-nSiXnIn, n is 1~4 integer, and Y is alkenyl group, and X is selected from Cl, methoxyl group OMe, ethyoxyl
OEt or trimethylsiloxy group OSiMe3；
Source of aluminium is selected from least one of sodium aluminate, aluminium hydroxide, aluminum sulfate, aluminum nitrate or aluminium chloride；
The alkali is selected from quaternary ammonium base, using alkali metal or alkali earth metal as at least one of alkali of cation；
Silicon source is with SiO2Meter, silicon source is with Al2O3Meter, alkali silicon mol ratio alkali/SiO2=0~0.3, silica alumina ratio SiO2/
Al2O3=25~85.
In above-mentioned technical proposal, the preferred alkali/SiO of alkali silicon mol ratio2=0.02~0.3, more preferably alkali/SiO2=0.03~
0.22, more preferably alkali/SiO2=0.04~0.18, most preferably alkali/SiO2=0.06~0.12.
In above-mentioned technical proposal, the preferred SiO of silica alumina ratio2/Al2O3=25~60, more preferably SiO2/Al2O3=30~
50。
In above-mentioned technical proposal, formula Y4-nSiXnIn, Y is preferably methyl, ethyl or propyl group.
In above-mentioned technical proposal, silicon source is preferably at least one of Ludox, smoke silica gel.
In above-mentioned technical proposal, the quaternary ammonium base is selected from TMAH, tetraethyl ammonium hydroxide, tetrapropyl hydrogen-oxygen
Change ammonium, TBAH, N, N, N- front three adamantyl ammonium hydroxide or dimethyl diethyl ammonium hydroxide.
In above-mentioned technical proposal, alkali is preferably at least one of NaOH or KOH.
In above-mentioned technical proposal, the crystal grain diameter of the Beta molecular sieves is 10~200 nanometers.
In above-mentioned technical proposal, the silica alumina ratio SiO of the Beta molecular sieves2/Al2O3=15~80.
In the inventive method, when using sodium aluminate, (composition of sodium aluminate is according to Al2O3And Na2O form represents) it is silicon source
When, alkali can be brought into, now no longer can separately add alkali source.But use the aluminium selected from aluminium hydroxide, aluminum sulfate, aluminum nitrate or aluminium chloride
When salt is silicon source, then need to add alkali source.The computational methods of alkali silicon mol ratio are：In alkali and silicon source in alkali silicon mol ratio=silicon source
Silicon mol ratio+alkali source in alkali and silicon source in silicon mol ratio.Such as when using Ludox as silicon source, sodium aluminate
(Al2O343.0 weight %, Na2The weight % of O 35.0) be silicon source, sodium hydroxide be alkali source, then alkali silicon mol ratio=2 × sodium aluminate
The material of silicon in amount/Ludox of the material of amount+sodium hydroxide of the material of silicon in amount/Ludox of the material of middle sodium oxide molybdena
Amount；When to use Ludox for silicon source, aluminum nitrate be silicon source, sodium hydroxide is alkali source, then the thing of alkali silicon mol ratio=sodium hydroxide
The amount of the material of silicon in amount/Ludox of matter.The calculating of this alkali is also that aluminium hydroxide and aluminium salt exist according to what is calculated after roasting
It is exactly Al after roasting2O3, alkali is equivalently employed without, so needing exogenously added alkali.And then show as Al after sodium aluminate roasting2O3And Na2O,
Therefore exogenously added alkali is not had to.
State Beta molecular sieves are synthesized described in the inventive method, refer to synthesize according to hydrothermal crystallization method known in the art
, the Beta molecular sieves of not fired removed template method.For example, it is directed to the mixed of agent, silicon compound, aluminium compound, alkali and water
Compound crystallization, and solid product separated, is dried, it can both obtain the Beta molecular sieves of the synthesis state.Wherein, silicon compound,
Aluminium compound, alkali, the mol ratio of directed agents and water are：1:(0.001~0.07):(0.05~0.30):(0.02~2.0):(6
~50), preferred scope 1:(0.01~0.067):(0.05~0.25):(0.05~0.30):(10~30).Hydrothermal crystallizing bar
Part includes：130~210 DEG C of crystallization temperature, preferably 150~180 DEG C；Crystallization time 10 hours~10 days, preferably 1~5 day.It is described
Silicon compound is selected from least one of silicic acid, silica gel, Ludox, silicic acid tetraalkyl ester, sodium metasilicate, waterglass or white carbon；
The aluminium compound in aluminium hydroxide, sodium aluminate, aluminium alcoholates, aluminum nitrate, aluminum sulfate, kaolin or montmorillonite at least one
Kind；The alkali is selected from the alkali using alkali metal or alkaline-earth metal as cation；The directed agents are selected from tetraethyl ammonium hydroxide and four
At least one of ethyl phosphonium bromide ammonium.
In the inventive method, the straight forming of the synthesis state Beta molecular sieves and silicon source, silicon source and alkali, which can use, to be squeezed
Go out the method for forming.Wherein it is possible to add pore creating material, the pore creating material be selected from sesbania powder, methylcellulose, polyethers (such as polyethylene glycol,
At least one of P123, F127).The mass ratio for synthesizing the silica in state Beta molecular sieves and pore creating material is 1:(0.005~
0.2), preferably 1:(0.01~0.1).Catalyst after shaping is the cylinder of 0.3~1.2 centimetre of length, the cross section of cylinder
For circular, square, bunge bedstraw herb shape, cloverleaf pattern, annular or star, cross section maximum radial dimension is 0.08~0.3 centimetre.Urge
Agent can also carry out ammonium exchange, steam treatment.
The preparation method of the catalyst containing P is in the present invention：In terms of parts by weight, by 1 part of Beta molecular sieve catalyst and 5
~50 parts of mass fractions 0.1~15%, preferably 0.3~5% phosphoric acid contacts 1~10 hour at 20~100 DEG C, by solid product
Separation, drying, roasting, obtain the Beta molecular sieve catalysts containing P.P can improve the stability at catalyst acid center.
The preparation method of the catalyst containing rare earth element is in the present invention：In terms of parts by weight, 1 part of Beta molecular sieve is urged
Agent and 5~50 parts of mass fractions 0.1~10%, the aqueous solution of preferably 0.3~5% rare earth metal salt connect at 20~100 DEG C
Touch 1~10 hour, solid product is separated, dry, is calcined, obtains the Beta molecular sieve catalysts containing rare earth element.Rare earth metal
Acidity can be adjusted.
Beta molecular sieve catalysts provided by the invention, in benzene and preparing ethylbenzene by liquid phase alkylation of ethylene, benzene and propylene liquid phase
It is good to be alkylated catalytic performance in preparing isopropylbenzene reaction, alkylation catalyst can be used as to be applied to benzene and ethylene liquid phase alkylation system
In ethylbenzene, benzene and the reaction of propylene liquid-phase alkylation preparing isopropylbenzene.
The present inventor uses Ludox or aluminum oxide to bond by largely testing discovery, prior art
Agent, catalyst strength is too high when consumption of binder is big, molecular sieve content is low, catalytic activity is low；Consumption of binder hour catalyst
Low intensity, efflorescence are serious.And secondary crystallization is long the time required to preparing Adhesive-free Molecular Sieve；Also, although prior art is claimed
Adhesive-free Molecular Sieve compression strength made from secondary crystallization is high, still, it was found by the inventors of the present invention that in benzene and ethene liquid phase
In alkylation ethylbenzene processed and the fixed bed reaction of benzene and propylene liquid-phase alkylation preparing isopropylbenzene (cumene), the compression strength of catalyst
It is not the higher the better.When the compression strength of catalyst is more than 120N/cm, for example, 130N/cm, the catalytic of catalyst now
Can be significantly lower than the catalyst that compression strength is 120N/cm.Therefore, it was found by the inventors of the present invention that for benzene and ethene and benzene
With the compression strength of propylene liquid-phase alkylation preparing ethylbenzene by reaction, the Beta molecular sieve catalysts of isopropylbenzene should control 60~
Between 120N/cm, preferably compression strength is 65~100N/cm, and more preferably compression strength is 65~90N/cm.In order to obtain so
The Beta molecular sieve catalysts of compression strength, it was found by the inventors of the present invention that when silicon source (such as Ludox) and silicon source (such as aluminium
Sour sodium) the in-situ preparation Alusil that chemically reacts can occur in the basic conditions, course of reaction is very fast, it is only necessary to which 5 minutes are i.e. anti-
Should be complete, the sial adhesiveness of generation is big, and molecular sieve is crosslinked together.According to this characteristic of Alusil, using Alusil
As binding agent, it is only necessary to which the binding agent no more than 5 weight % is the shaping that catalyst can be achieved, also, gained catalyst is anti-
Compressive Strength is higher than 60N/cm, preferably 60~120N/cm, is particularly suitable as benzene and the catalyst of olefin liquid phase alkylation, obtains
Preferable technique effect.
Heretofore described Beta molecular sieve catalysts, the method for molecular sieve silica alumina ratio chemical analysis determine.
Heretofore described Beta molecular sieve catalysts, the compression strength of molecular sieve using pressure testing machine to roasting after
Catalyst tested, method of testing is：The catalyst granules that length L is 0.4~0.6 centimetre is chosen, by catalyst granules
It is laterally disposed on test platform, gradually increases pressure to catalyst and be crushed, instrument is recorded when catalyst is crushed and applied automatically
The pressure F (newton, N) added, F and L ratio (F/L) are the compression strength of single catalyst.10 catalyst of test resist
The compression strength that its average value is the catalyst is taken after Compressive Strength.
Binder content computational methods are in heretofore described Beta molecular sieve catalysts：Synthesize state Beta molecular sieves
Weight after being calcined 5 hours in 550 DEG C, air atmosphere is A, during straight forming silicon source, silicon source and alkali source used 550 DEG C,
Weight after being calcined 5 hours in air atmosphere is B, then content=B/ (A+B) × 100% of binding agent.
Brief description of the drawings
Fig. 1 is【Embodiment 1】The XRD spectra of the Beta molecular sieve catalysts of preparation.Diffraction maximum is can be seen that from its spectrogram
It is coincide with the characteristic diffraction peak of Beta molecular sieves.
Embodiment
【Embodiment 1】
A) preparation of state Beta molecular sieves is synthesized：Using alkaline silica sol, Patent alum, tetraethyl ammonium hydroxide
(TEAOH) and water is synthesis material, is according to material proportion (mol ratio) by above-mentioned raw materials：
SiO2/Al2O3=25
TEAOH/SiO2=0.20
H2O/SiO2=18
After well mixed, it is fitted into stainless steel cauldron, under agitation in 150 DEG C of crystallization 5 days.Mistake after crystallization terminates
Filter, wash, being dried to obtain the Beta molecular sieves of synthesis state.By being calcined 5 hours test synthesis states in 550 DEG C, air atmosphere
The weight-loss ratio of Beta molecular sieves is 13.1 weight %.
B) alkaline silica sol (SiO is used240.0 weight %) it is silicon source, sodium aluminate (Al2O343.0 weight %, Na2O
35.0 weight %) it is silicon source, by 48.1 grams of synthesis state Beta molecular sieves in 0.25 gram of sodium aluminate and step a), sesbania powder
0.5616 gram well mixed, adds alkaline silica sol (SiO240.0 weight %) 4.5 grams.Silica alumina ratio SiO2/Al2O3=
28.5, alkali silicon mol ratio alkali/SiO2=0.094, it is 95.4 weight %, bonding to prepare Beta molecular sieve contents by extruded moulding
The content of agent is 4.6 weight %, cross section is circular strip molecular sieve catalyst precursor I.
C) obtained Beta molecular sieve catalysts precursor I in step b) is calcined 6 hours under 550 DEG C, air atmosphere
Beta molecular sieve catalyst precursor IIs.
D) by ammonium nitrate of the obtained Beta molecular sieve catalysts precursor II at 90 DEG C with mass fraction 15% in step c)
Solution is contacted 3 times, 1 hour every time, and solid product is separated, dried, is calcined to obtain Beta molecular sieve catalysts.
The XRD spectra of product is as shown in Figure 1.The compression strength of Beta molecular sieve catalysts is 82N/cm.
【Embodiment 2】
Together【Embodiment 1】, simply：
B) will 59.6 grams of synthesis state Beta molecular sieves, alkaline silica sol (SiO240.0 weight %) 4.5 grams, sesbania powder
1.05 grams, sodium aluminate (Al2O343.0 weight %, Na2The weight % of O 35.0) 0.25 gram of well mixed, silica alumina ratio SiO2/
Al2O3=28.5, alkali silicon mol ratio alkali/SiO2=0.094, it is 96.3 weights to prepare Beta molecular sieve contents by extruded moulding
Measure %, the strip molecular sieve catalyst precursor that the content of binding agent is 3.7 weight %, cross section is bunge bedstraw herb.
C) obtained Beta molecular sieve catalysts precursor I in step b) is calcined 6 hours under 550 DEG C, air atmosphere
Beta molecular sieve catalyst precursor IIs.
D) by ammonium nitrate of the obtained Beta molecular sieve catalysts precursor II at 60 DEG C with mass fraction 15% in step c)
Solution is contacted 3 times, 1 hour every time, and solid product is separated, dried, is calcined to obtain Beta molecular sieve catalysts.Product
XRD spectra is similar to Fig. 1.The compression strength of Beta molecular sieve catalysts is 82N/cm.
【Embodiment 3】
Together【Embodiment 1】, simply：
B) will 77.0 grams of synthesis state Beta molecular sieves, alkaline silica sol (SiO240.0 weight %) 4.5 grams, sesbania powder
1.05 grams, sodium aluminate (Al2O343.0 weight %, Na2The weight % of O 35.0) 0.25 gram it is well mixed.Silica alumina ratio SiO2/
Al2O3=28.5, alkali silicon mol ratio alkali/SiO2=0.094, it is 97.1 weights to prepare Beta molecular sieve contents by extruded moulding
Measure %, the strip molecular sieve catalyst precursor that the content of binding agent is 2.9 weight %, cross section is bunge bedstraw herb.
C) obtained Beta molecular sieve catalysts precursor I in step b) is calcined 6 hours under 550 DEG C, air atmosphere
Beta molecular sieve catalyst precursor IIs.
D) by ammonium nitrate of the obtained Beta molecular sieve catalysts precursor II at 60 DEG C with mass fraction 15% in step c)
Solution is contacted 3 times, 1 hour every time, and solid product is separated, dried, is calcined to obtain Beta molecular sieve catalysts.Product
XRD spectra is similar to Fig. 1.The compression strength of Beta molecular sieve catalysts is 69N/cm.
【Embodiment 4】
Together【Embodiment 1】, simply：
B) will 59.6 grams of synthesis state Beta molecular sieves, alkaline silica sol (SiO240.0 weight %) 4.5 grams, sesbania powder
1.05 grams, sodium aluminate (Al2O343.0 weight %, Na2The weight % of O 35.0) 0.17 gram it is well mixed.Silica alumina ratio SiO2/
Al2O3=41.9, alkali silicon mol ratio alkali/SiO2=0.064, it is 96.4 weights to prepare Beta molecular sieve contents by extruded moulding
Measure %, the strip molecular sieve catalyst precursor that the content of binding agent is 3.6 weight %, cross section is bunge bedstraw herb.
C) obtained Beta molecular sieve catalysts precursor I in step b) is calcined 6 hours under 550 DEG C, air atmosphere
Beta molecular sieve catalyst precursor IIs.
D) by ammonium nitrate of the obtained Beta molecular sieve catalysts precursor II at 60 DEG C with mass fraction 15% in step c)
Solution is contacted 3 times, 1 hour every time, and solid product is separated, dried, is calcined to obtain Beta molecular sieve catalysts.Product
XRD spectra is similar to Fig. 1.The compression strength of Beta molecular sieve catalysts is 76N/cm.
【Embodiment 5】
Together【Embodiment 1】, simply：
B) will 77.0 grams of synthesis state Beta molecular sieves, smoke silica gel (SiO297.0 weight %) 2.0 grams, sesbania powder 1.5
Gram, sodium aluminate (Al2O343.0 weight %, Na2The weight % of O 35.0) 0.3 gram it is well mixed.Silica alumina ratio SiO2/Al2O3=
25.6, alkali silicon mol ratio alkali/SiO2=0.105, it is 96.8 weight %, bonding to prepare Beta molecular sieve contents by extruded moulding
The strip molecular sieve catalyst precursor that the content of agent is 3.2 weight %, cross section is bunge bedstraw herb.
C) obtained Beta molecular sieve catalysts precursor I in step b) is calcined 6 hours under 550 DEG C, air atmosphere
Beta molecular sieve catalyst precursor IIs.
D) by ammonium nitrate of the obtained Beta molecular sieve catalysts precursor II at 60 DEG C with mass fraction 15% in step c)
Solution is contacted 3 times, 1 hour every time, and solid product is separated, dried, is calcined to obtain Beta molecular sieve catalysts.Product
XRD spectra is similar to Fig. 1.The compression strength of Beta molecular sieve catalysts is 71N/cm.
【Embodiment 6】
Together【Embodiment 1】, simply：
B) will 59.6 grams of synthesis state Beta molecular sieves, alkaline silica sol (SiO240.0 weight %) 2.425 grams, smoke silicon
Glue (SiO297.0 weight %) 1.0 grams, 1.5 grams of sesbania powder, aluminum sulfate (Al2(SO4)3·18H2O, Al2O315.2 weight %)
0.868 gram, 0.135 gram of sodium hydroxide (the weight % of NaOH 96.0) it is well mixed.Silica alumina ratio SiO2/Al2O3=25, alkali silicon
Mol ratio alkali/SiO2=0.129, content of the Beta molecular sieve contents for 95.8 weight %, binding agent is prepared by extruded moulding
For 4.2 weight %, the strip molecular sieve catalyst precursor that cross section is bunge bedstraw herb.
C) obtained Beta molecular sieve catalysts precursor I in step b) is calcined 6 hours under 550 DEG C, air atmosphere
Beta molecular sieve catalyst precursor IIs.
D) by ammonium nitrate of the obtained Beta molecular sieve catalysts precursor II at 60 DEG C with mass fraction 15% in step c)
Solution is contacted 3 times, 1 hour every time, and solid product is separated, dried, is calcined to obtain Beta molecular sieve catalysts.Product
XRD spectra is similar to Fig. 1.The compression strength of Beta molecular sieve catalysts is 67N/cm.
【Embodiment 7】
Together【Embodiment 1】, simply：
B) will 59.6 grams of synthesis state Beta molecular sieves, alkaline silica sol (SiO240.0 weight %) 4.5 grams, sesbania powder
1.05 grams, sodium aluminate (Al2O343.0 weight %, Na2The weight % of O 35.0) 0.25 gram, the sodium hydroxide (weights of NaOH 96.0
Measure %) 0.02 gram it is well mixed.Silica alumina ratio SiO2/Al2O3=28.5, alkali silicon mol ratio alkali/SiO2=0.115, by squeezing
Bar shaping prepares that Beta molecular sieve contents are 96.3 weight %, the content of binding agent is 3.7 weight %, cross section is bunge bedstraw herb
Strip molecular sieve catalyst precursor.
C) obtained Beta molecular sieve catalysts precursor I in step b) is calcined 6 hours under 550 DEG C, air atmosphere
Beta molecular sieve catalyst precursor IIs.
D) by ammonium nitrate of the obtained Beta molecular sieve catalysts precursor II at 60 DEG C with mass fraction 15% in step c)
Solution is contacted 3 times, 1 hour every time, and solid product is separated, dried, is calcined to obtain Beta molecular sieve catalysts.Product
XRD spectra is similar to Fig. 1.The compression strength of Beta molecular sieve catalysts is 86N/cm.
【Embodiment 8】
Together【Embodiment 1】, simply：
B) 0.05 gram of sodium hydroxide, silica alumina ratio SiO are added2/Al2O3=28.5, alkali silicon mol ratio alkali/SiO2=
0.146, prepare that Beta molecular sieve contents are 95.3 weight %, the content of binding agent is 4.7 weight %, transversal by extruded moulding
Face is circular strip molecular sieve catalyst precursor.
The XRD spectra of product is similar to Fig. 1.The compression strength of Beta molecular sieve catalysts is 88N/cm.
【Embodiment 9】
Together【Embodiment 1】, simply：
B) sodium hydroxide is added, and controls silica alumina ratio SiO2/Al2O3=60, alkali silicon mol ratio alkali/SiO2=0.10,
Prepare that Beta molecular sieve contents are 96.9 weight %, the content of binding agent is 3.1 weight %, cross section is round by extruded moulding
The strip molecular sieve catalyst precursor of shape.
The XRD spectra of product is similar to Fig. 1.The compression strength of Beta molecular sieve catalysts is 77N/cm.
【Embodiment 10】
Together【Embodiment 1】, simply：
A) material proportion (mol ratio) of reactant mixture is：
SiO2/Al2O3=40
TEAOH/SiO2=0.15
H2O/SiO2=18
The weight-loss ratio of test synthesis state Beta molecular sieves is 12.4 weight %.
B) silica alumina ratio SiO2/Al2O3=28.5, alkali silicon mol ratio alkali/SiO2=0.094, prepared by extruded moulding
Beta molecular sieve contents are 97.1 weight %, the content of binding agent is 2.9 weight %, cross section is that circular strip molecular sieve is urged
Agent precursor.
The XRD spectra of product is similar to Fig. 1.The compression strength of Beta molecular sieve catalysts is 82N/cm.
【Embodiment 11】
Together【Embodiment 1】, simply by the phosphorus of 30 grams of obtained Beta molecular sieve catalysts in step d) and mass fraction 2%
300 grams of acid is contacted 3 hours at 30 DEG C, and solid product is separated, dry, is calcined, obtains the Beta molecular sieve catalysts containing P.P content
For 0.1 weight %.The XRD spectra of product is similar to Fig. 1.The compression strength of Beta molecular sieve catalysts is 80N/cm.
【Embodiment 12】
Together【Embodiment 1】, simply by the nitre of 30 grams of obtained Beta molecular sieve catalysts in step d) and mass fraction 3%
Sour 450 grams of the lanthanum aqueous solution is contacted 2 hours at 75 DEG C, and solid product is separated, dry, is calcined, obtains the Beta molecules containing lanthanum element
Sieve catalyst.It is 0.17 weight % to measure lanthanum content by ICP.The XRD spectra of product is similar to Fig. 1.Beta molecular sieve catalytics
The compression strength of agent is 85N/cm.
【Embodiment 13】
Together【Embodiment 11】, simply further by the nitric acid of 20 grams of the Beta molecular sieve catalysts containing P and mass fraction 3%
300 grams of the lanthanum aqueous solution is contacted 2 hours at 95 DEG C, and solid product is separated, dry, is calcined, obtains the Beta molecules containing P and lanthanum element
Sieve catalyst.It is 0.2 weight % to measure lanthanum content by ICP.The XRD spectra of product is similar to Fig. 1.Beta molecular sieve catalysts
Compression strength be 78N/cm.
【Comparative example 1】
Together【Embodiment 1】, Ludox is simply used as binding agent：
B) will 48.1 grams of synthesis state Beta molecular sieves, alkaline silica sol (SiO240.0 weight %) 5.04 grams, sesbania powder
0.5616 gram is well mixed, by extruded moulding prepare Beta molecular sieve contents be 95.4 weight %, the content of binding agent be 4.6
Weight %, the strip molecular sieve catalyst precursor that cross section is bunge bedstraw herb.
The XRD spectra of product is as shown in Figure 1.The compression strength of Beta molecular sieve catalysts is 32N/cm.
【Comparative example 2】
Together【Embodiment 1】, aluminum oxide is simply used as binding agent：
B) will 48.1 grams of synthesis state Beta molecular sieves, aluminum oxide (Al2O396 weight %) 2.1 grams, 0.5616 gram of sesbania powder
It is well mixed, by extruded moulding prepare Beta molecular sieve contents be 95.4 weight %, the content of binding agent be 4.6 weight %,
Cross section is the strip molecular sieve catalyst precursor of bunge bedstraw herb.
The XRD spectra of product is as shown in Figure 1.The compression strength of Beta molecular sieve catalysts is 41N/cm.
【Comparative example 3】
Method according to document CN105439164A prepares binder free Beta molecular sieve catalysts：Will【Embodiment 1】In
Beta molecular sieves and white carbon, Ludox (SiO240.0 weight %), sodium aluminate, sodium metasilicate mixed-forming, roasting, obtain former
Material ratio is 4.5Na2O：5Al2O3：100SiO2Presoma, Beta contents 50 weight the %, (TEA/SiO in TEAOH solution2
=0.25, water/SiO2=5), 160 DEG C of crystallization 96h take out, and after 120 drying, 2h are calcined at 400 DEG C, 550 DEG C of roasting 3h are obtained
Beta molecular sieve catalysts.
The XRD spectra of product is similar to Fig. 1, and the content of molecular sieve is 93.6 weight %, compression strength 35N/ in product
cm。
【Embodiment 14】
Will【Embodiment 1】In catalyst be used for continuous fixed bed benzene and ethylene liquid phase alkylation and react, reaction condition is：
175 DEG C, pressure 3.5MPa of temperature, benzene/alkene charge proportion 2, Ethylene mass air speed 6h-1, after reaction is carried out continuously 5h, ethene conversion
Rate is 70.6%.
【Comparative example 4】
Will【Comparative example 3】Middle gained catalyst is used for continuous fixed bed benzene and reacted with ethylene liquid phase alkylation, reaction condition
For：175 DEG C, pressure 3.5MPa of temperature, benzene/alkene charge proportion 2, Ethylene mass air speed 6h-1, after reaction is carried out continuously 5h, ethene
Conversion ratio is only 48.8%.
Claims (23)
1. a kind of Beta molecular sieve catalysts, in terms of parts by weight, including following component：
A) 92~99 parts of Beta molecular sieves；
B) 1~8 part of sial glue caking agent；
The step of sial glue caking agent is contacted by silicon source, silicon source and alkali obtains；Silicon source is with SiO2Meter, silicon source with
Al2O3Meter, alkali silicon mol ratio alkali/SiO2=0~0.3, silica alumina ratio SiO2/Al2O3=25~85.
2. Beta molecular sieve catalysts according to claim 1, it is characterised in that alkali silicon mol ratio alkali/SiO2=0.02~
0.3。
3. Beta molecular sieve catalysts according to claim 2, it is characterised in that alkali silicon mol ratio alkali/SiO2=0.03~
0.22。
4. Beta molecular sieve catalysts according to claim 3, it is characterised in that alkali silicon mol ratio alkali/SiO2=0.04~
0.18。
5. Beta molecular sieve catalysts according to claim 1, it is characterised in that silica alumina ratio SiO2/Al2O3=25~
60。
6. Beta molecular sieve catalysts according to claim 1, it is characterised in that the silicon source is selected from Ludox, smoke silicon
Glue, waterglass or formula are Y4-nSiXnAt least one of silicon-containing compound；Formula Y4-nSiXnIn, n be 1~4 integer, Y
For alkenyl group, X is selected from Cl, methoxyl group OMe, ethyoxyl OEt or trimethylsiloxy group OSiMe3；
Source of aluminium is selected from least one of sodium aluminate, aluminium hydroxide, aluminum sulfate, aluminum nitrate or aluminium chloride；
The alkali is selected from quaternary ammonium base, using alkali metal or alkali earth metal as at least one of alkali of cation.
7. Beta molecular sieve catalysts according to claim 6, it is characterised in that the formula Y4-nSiXnIn, Y be methyl,
Ethyl or propyl group；The quaternary ammonium base is selected from TMAH, tetraethyl ammonium hydroxide, TPAOH, the tetrabutyl
Ammonium hydroxide, N, N, N- front three adamantyl ammonium hydroxide or dimethyl diethyl ammonium hydroxide.
8. Beta molecular sieve catalysts according to claim 1, it is characterised in that in terms of parts by weight, Beta molecular sieves
Content is 95~99 parts, and the content of sial glue caking agent is 1~5 part.
9. Beta molecular sieve catalysts according to claim 8, it is characterised in that in terms of parts by weight, Beta molecular sieves
Content is 96~99 parts, and the content of sial glue caking agent is 1~4 part.
10. Beta molecular sieve catalysts according to claim 1, it is characterised in that the silicon source is selected from Ludox or smoke
At least one of silica gel；The alkali is selected from least one of NaOH or KOH.
11. Beta molecular sieve catalysts according to claim 1, it is characterised in that the crystal grain diameter of the Beta molecular sieves
For 10~200 nanometers, the silica alumina ratio SiO of Beta molecular sieves2/Al2O3=15~80.
12. Beta molecular sieve catalysts according to claim 1, it is characterised in that the Beta molecular sieve catalysts resist
Compressive Strength be 60~120 newton/centimetre.
13. the Beta molecular sieve catalysts according to claim 12, it is characterised in that the Beta molecular sieve catalysts resist
Compressive Strength be 65~100 newton/centimetre.
14. the Beta molecular sieve catalysts according to claim 13, it is characterised in that the Beta molecular sieve catalysts resist
Compressive Strength be 65~90 newton/centimetre.
15. Beta molecular sieve catalysts according to claim 1, it is characterised in that in terms of parts by weight, the catalyst bag
Include 0~0.5 part of phosphorus.
16. Beta molecular sieve catalysts according to claim 1, it is characterised in that in terms of parts by weight, the catalyst bag
Include 0~0.5 part of thulium.
17. the Beta molecular sieve catalysts according to claim 16, it is characterised in that the thulium be selected from yttrium,
At least one of lanthanum, cerium or neodymium.
18. a kind of preparation method of Beta molecular sieve catalysts, comprises the following steps：
A) synthesis state Beta molecular sieves are provided；
B) synthesis state Beta molecular sieves, silicon source, silicon source and the alkali straight forming obtain the Beta molecular sieve catalysts；
Wherein, the silicon source is Y selected from Ludox, smoke silica gel, waterglass or formula4-nSiXnSilicon-containing compound at least
It is a kind of；Formula Y4-nSiXnIn, n is 1~4 integer, and Y is alkenyl group, and X is selected from Cl, methoxyl group OMe, ethyoxyl OEt or three
Methyl siloxy OSiMe3；
Source of aluminium is selected from least one of sodium aluminate, aluminium hydroxide, aluminum sulfate, aluminum nitrate or aluminium chloride；
The alkali is selected from quaternary ammonium base, using alkali metal or alkali earth metal as at least one of alkali of cation；
Silicon source is with SiO2Meter, silicon source is with Al2O3Meter, alkali silicon mol ratio alkali/SiO2=0~0.3, silica alumina ratio SiO2/Al2O3=
25~85.
19. the preparation method of Beta molecular sieve catalysts according to claim 18, it is characterised in that alkali silicon mol ratio alkali/
SiO2=0.02~0.3.
20. the preparation method of Beta molecular sieve catalysts according to claim 19, it is characterised in that alkali silicon mol ratio alkali/
SiO2=0.03~0.22.
21. the preparation method of Beta molecular sieve catalysts according to claim 20, it is characterised in that alkali silicon mol ratio alkali/
SiO2=0.04~0.18.
22. the preparation method of Beta molecular sieve catalysts according to claim 18, it is characterised in that silica alumina ratio SiO2/
Al2O3=25~60.
23. the Beta molecular sieve catalysts described in claim 1~17, or synthesized according to claim 18~22 methods described
Beta molecular sieve catalysts it is anti-in benzene and preparing ethylbenzene by liquid phase alkylation of ethylene or benzene and propylene liquid-phase alkylation preparing isopropylbenzene
Middle it should apply.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4169111A (en) * | 1978-02-02 | 1979-09-25 | Union Oil Company Of California | Manufacture of ethylbenzene |
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2016
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4169111A (en) * | 1978-02-02 | 1979-09-25 | Union Oil Company Of California | Manufacture of ethylbenzene |
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