CN107511168A - The preparation method of Adhesive-free Molecular Sieve catalyst - Google Patents
The preparation method of Adhesive-free Molecular Sieve catalyst Download PDFInfo
- Publication number
- CN107511168A CN107511168A CN201610440415.XA CN201610440415A CN107511168A CN 107511168 A CN107511168 A CN 107511168A CN 201610440415 A CN201610440415 A CN 201610440415A CN 107511168 A CN107511168 A CN 107511168A
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- sieve catalyst
- adhesive
- preparation
- free
- 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.)
- Granted
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
- B01J29/7038—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
-
- 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
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
-
- 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
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
- C07C6/08—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond
- C07C6/12—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond of exclusively hydrocarbons containing a six-membered aromatic ring
- C07C6/126—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond of exclusively hydrocarbons containing a six-membered aromatic ring of more than one hydrocarbon
-
- 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
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/38—Base treatment
-
- 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
- C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
-
- 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
Abstract
The present invention relates to a kind of preparation method of Adhesive-free Molecular Sieve catalyst, mainly solves prior art and the problem of Adhesive-free Molecular Sieve catalyst preparation process is complicated, and binder content is high, catalytic performance difference be present.The present invention is by using comprising the following steps：Contacted by molecular sieve catalyst precursor and with least one compound that the binding agent in the molecular sieve catalyst precursor chemically reacts for the solution of solute, solid product is separated afterwards, dried, is calcined molecular sieve catalyst technical scheme, preferably solves the problem, in the industrial production available for Adhesive-free Molecular Sieve catalyst.
Description
Technical field
The present invention relates to a kind of preparation method of Adhesive-free Molecular Sieve catalyst.
Background technology
Industrially, porous inorganic material is widely used as catalyst and catalyst carrier.Porous material has relatively
High ratio surface and unimpeded pore passage structure, therefore be good catalysis material or catalyst carrier.Porous material substantially can be with
Including：Unformed porous material, crystalline molecular sieve and stratified material of modification etc..The nuance of these material structures, in advance
Show themselves in the catalysis of material and the gross differences of absorption property etc., and can for characterizing the various of them
The difference in performance is observed, such as the changeability of their pattern, specific surface area, void size and these sizes.
The basic skeleton structure of crystalline microporous zeolite is to be based on rigid three-dimensional TO4(SiO4, AlO4Deng) cellular construction；
TO in this structure4It is that oxygen atom, skeleton tetrahedron such as AlO are shared with tetrahedral manner4Charge balance be by surface cation
Such as Na+、H+Presence keep.The skeleton property of zeolite can be changed by cation exchange mode as can be seen here.Meanwhile
There is the pore canal system that abundant, aperture are certain in the structure of zeolite, the interlaced formation tridimensional network in these ducts,
And water in duct or organic matter be removed after its skeleton remain to be stabilized (US 4439409).It is based on said structure,
Zeolite not only has good catalytic activity, excellent shape selectivity to various organic reactions and good choosing can be achieved by modified
Selecting property (US 6162416, US 4954325, US 5362697).
The specific structure of molecular sieve is to determine that X-ray diffraction spectrogram (XRD) is by X- by X-ray diffraction spectrogram (XRD)
Ray powder diffractometer determines, and uses Cu-K alpha rays source, nickel filter.Different zeolite molecular sieves, its XRD spectra feature is not
Together.Existing molecular sieve, such as type A zeolite (US2882243), y-type zeolite (US3130007), PSH-3 molecular sieves
(US4439409), ZSM-11 molecular sieves (US3709979), ZSM-12 molecular sieves (US3832449), ZSM-23 molecular screen
(US4076842), ZSM-35 molecular sieve (US4016245), MCM-22 molecular sieves (US4954325) etc. are respectively provided with features
XRD spectra.
Molecular sieve, found from the mankind so far, due to its good heat endurance, hydrothermal stability；Regulatable acidity；Solely
The features such as special pore passage structure, have been widely used in the fields such as adsorbing separation, ion exchange, heterogeneous catalysis.Such as MWW structures point
The sub application for sieving MCM-22 in benzene alkylation reaction, MFI structure molecular sieve ZSM-5 are in alkylation alkylbenzene, methylbenzene shape-selective
The application of application, FAU structure molecular screens Y in crude oil catalytic pyrolysis in disproportionation paraxylene processed, preparing propylene from methanol reaction,
The application of CHA structure molecular sieve SSZ-13 in terms of vehicle maintenance service, etc..
But molecular sieve is generally powdered, particle diameter is from tens nanometers to several microns.And industrial production interrupts reactor body
Product is huge, has strict demand to catalyst size：Fixed bed needs bulk catalyst 2-15mm；Fluid bed and slurry bed system then need
The particle diameter of catalyst is in micron order.Gap great disparity between molecular sieve crystal and industrial production used catalyst particle diameter, thus
Need to be molded molecular sieve crystal and meet the molecular sieve catalyst of demand of industrial production to obtain.First according to the spy of production technology
The suitable reactor of point selection, redesigns suitable catalyst shape, size, pore structure etc., and the corresponding shaping of finally selection is set
It is standby with moulding process by system with molecular sieve for preparing into preformed catalyst.In order to make molecular sieve powder shaping need to add binding agent.In addition,
To meet that the operation needs of forming process will also add the additives such as lubricant, pore creating material, plasticizer.These additives add
Enter, the addition of especially binding agent can more cover the activated centre of molecular sieve, while can be used as active component in limiting catalyst
Molecular sieve content, the content of the molecular sieve in the molecular sieve catalyst of general merchandise is less than 80 mass %.Therefore, in business
The quantity in the activated centre in the molecular sieve catalyst of the shaping of product is far below the molecular sieve before shaping.
In order to overcome the problem of containing binding agent, activated centre in catalyst less, document CN102039157A discloses one
The preparation method of kind non-binder MCM-22 molecular sieve catalyst, crystalline substance is turned by gas phase binding agent is converted into MCM-22 molecules
Sieve.However, this method is up to 20~300 hours the time required to turning brilliant.Although it claims the binder free MCM-22 molecules of synthesis
Sieve intensity be up to 180 newton/, but it was found by the inventors of the present invention that catalyst strength catalytic performance is influenceed it is notable.Such as application
In the compression strength of the molecular sieve catalyst of fixed bed reactors it is not the higher the better, it is necessary to find suitable compression strength
It 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 has Adhesive-free Molecular Sieve catalyst preparation process and answered
Miscellaneous, binder content is high, the problem of catalytic performance difference.Molecular sieve catalyst containing binding agent is carried out into secondary crystallization to obtain without viscous
, required crystallization time length be present in the method for tying agent catalyst, crystallization not thoroughly, the problem of catalytic performance is low, there is provided it is a kind of newly
The preparation method of Adhesive-free Molecular Sieve catalyst.This method short time can dissolve binding agent, completely removing, gained catalysis
Agent compression strength meets requirement of the fixed bed reactors to catalyst, is 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 Adhesive-free Molecular Sieve catalyst
Preparation method, comprise the following steps：By molecular sieve catalyst precursor and with the binding agent in the molecular sieve catalyst precursor
At least one compound to chemically react contacts for the solution of solute, afterwards separates solid product, dries, is calcined score
Sub- sieve catalyst.
In above-mentioned technical proposal, synthesis state molecular sieve is mixed with binding agent, is molded, before dry acquisition molecular sieve catalyst
Body；Preferably, the binding agent is selected from Ludox, smoke silica gel, waterglass, formula Y4-nSiXnSilicon-containing compound (n=1
~4, Y are alkyl, such as methyl, ethyl, propyl group, and X is hydrolyzable groups, such as Cl, methoxyl group OMe, ethyoxyl OEt, trimethyl
Siloxy OSiMe3Deng), at least one of aluminum oxide；In terms of the weight of the molecular sieve catalyst precursor after roasting, molecular sieve
The content of molecular sieve in catalyst precarsor is 40~90 weight %.Wherein, preferably, the molecule in molecular sieve catalyst precursor
The content of sieve is 60~85 weight %.It is in order that the compression strength of catalyst is maintained at optimal using above-mentioned technical proposal
In the range of.
Wherein, " binding agent " and " binding agent in molecular sieve catalyst precursor " is different." binding agent " is molecular sieve
Added before catalyst precarsor shaping, the binding agent mixed with synthesis state molecular sieve, such as Ludox, smoke silica gel." point
Binding agent in sub- sieve catalyst precursor " refers to the binding agent in the molecular sieve catalyst precursor after shaping, such as present invention in fact
Apply in example 1, after " binding agent (alkaline silica sol) " adds the molecular sieve catalyst mixing of synthesis state, through overmolding, drying, be converted into
" binding agent (amorphous silica) in molecular sieve catalyst precursor ".
State molecular sieve is synthesized described in above-mentioned technical proposal, refers to synthesize according to hydrothermal crystallization method known in the art
, the molecular sieve of not fired removed template method.For example, MCM-22 synthesis state molecular sieve synthesis, by Organic structure directing agent,
Silicon compound, aluminium compound, the mixture crystallization of alkali and water, and solid product separated, is dried, it can both obtain the synthesis state
Molecular sieve.Wherein, the mol ratio of silicon compound, aluminium compound, alkali, directed agents and water is：1:(0.01~0.07):(0.05
~0.30):(0.2~2.0):(6~50), preferred scope 1:(0.015~0.04):(0.06~0.20):(0.3~1.0):
(10~30).Hydrothermal crystallizing condition includes：130~210 DEG C of crystallization temperature, preferably 150~180 DEG C；Crystallization time 10 hours~
10 days, preferably 1~5 day.The silicon compound be selected from silicic acid, silica gel, Ludox, silicic acid tetraalkyl ester, sodium metasilicate, waterglass or
At least one of white carbon；The aluminium compound is selected from aluminium hydroxide, sodium aluminate, aluminium alcoholates, aluminum nitrate, aluminum sulfate, kaolin
Or at least one of montmorillonite；The alkali is selected from the alkali using alkali metal or alkaline-earth metal as cation；The directed agents are selected from
At least one of hexamethylene imine, piperidines or homopiperazine.
In above-mentioned technical proposal, the shaping can use extrusion moulding.Wherein it is possible to pore creating material is added, it is described to make
Hole agent is selected from least one of sesbania powder, methylcellulose, polyethers (such as polyethylene glycol, P123, F127).Synthesize state molecular sieve
In silica and pore creating material mass ratio be 1:(0.005~0.2), preferably 1:(0.01~0.1).Catalyst after shaping
For 0.3~1.2 centimetre of cylinder of length, the cross section of cylinder is circular, square, bunge bedstraw herb shape, cloverleaf pattern, annular or star
Shape, cross section maximum radial dimension are 0.08~0.3 centimetre.
In above-mentioned technical proposal, roasting uses this area conventional molecular sieve method of roasting, for example, oxygen-containing at 400~800 DEG C
Molecular sieve catalyst is calcined 3~10 hours to obtain under the atmosphere of gas.
In above-mentioned technical proposal, also comprise the following steps：Obtained molecular sieve catalyst is not higher than 7 at least in pH value
Contacted in a kind of solution or steam, solid product is separated afterwards, dry, is calcined.Preferably, the molecular sieve catalyst obtained exists
At least one solution or steam of the pH value not higher than 7 contact, and are implemented as, by the molecular sieve catalyst at 10~600 DEG C
Contacted 1~5 time, 10 minutes every time~3 hours with least one solution or steam of the pH value not higher than 7；More preferably, it is described
Solution includes the aqueous solution of ammonium salt, as ammonium nitrate, ammonium phosphate, ammonium oxalate the aqueous solution, the sour aqueous solution, such as oxalic acid, phosphoric acid
The aqueous solution of the aqueous solution, alkali salt or rare earth metal salt, such as the aqueous solution of lanthanum nitrate, the steam includes water vapour.Its
In, the pH value determines at ambient temperature.
In above-mentioned technical proposal, it is described with molecular sieve catalyst precursor at least one that chemically reacts of binding agent
Compound includes the aqueous solution of acid or the aqueous solution of alkali for the solution of solute；Preferably, including selected from inorganic acid, organic acid, season
Ammonium alkali, the aqueous solution using alkali metal or alkali earth metal as the alkali of cation；Preferably, the inorganic acid includes nitre
Acid, hydrochloric acid, phosphoric acid or sulfuric acid, the organic acid include formic acid, acetic acid, propionic acid, acrylic acid or ethanedioic acid, and the quaternary ammonium base includes
TMAH, tetraethyl ammonium hydroxide, TPAOH, TBAH, N, N, N- trimethyl Buddha's warrior attendants
Alkyl ammonium hydroxide or dimethyl diethyl ammonium hydroxide, the alkali using alkali metal or alkali earth metal as cation
Including NaOH or KOH.Using the above method, sent out by the catalyst containing binding agent and with the binding agent in molecular sieve catalyst precursor
At least one compound of biochemical reaction contacts for the solution of solute, can simply, it is efficient, fully by binder component from
Removed in catalyst, soap-free emulsion polymeization molecular sieve catalyst is made.
In above-mentioned technical proposal, it is described with molecular sieve catalyst precursor at least one that chemically reacts of binding agent
Compound be solute solution in the mass fraction of solute be 0.001%~5%；Preferably 0.01%-3%；Preferably
0.01%-1%；Preferably 0.03%-0.9%；Best 0.05%-0.7%.The mass fraction of solute is controlled in above-mentioned model
In enclosing, while quick removal binding agent is realized, the etching to molecular sieve crystal is avoided, and protect the compression strength of catalyst
Hold in optimal scope, obtain optimal Adhesive-free Molecular Sieve catalyst.
In above-mentioned technical proposal, it is described with molecular sieve catalyst precursor at least one that chemically reacts of binding agent
Compound is the solution of solute and the mass ratio of molecular sieve catalyst precursor is 5~100：1；Preferably 10-50:1；Preferably
10-40:1；Best 10-30:1.By the control of the mass ratio of solution and molecular sieve catalyst precursor within the above range, realizing
While quick removal binding agent, the etching to molecular sieve crystal is avoided, and the compression strength of catalyst is maintained at optimal
In the range of, obtain optimal Adhesive-free Molecular Sieve catalyst.
In above-mentioned technical proposal, the Contact Temperature is not higher than 240 DEG C, and the time of contact is -2 days 10 minutes；Compared with
Alright, the Contact Temperature is not higher than 190 DEG C, and time of contact is -12 hours 20 minutes；Preferably, the Contact Temperature is
60-180 DEG C, time of contact is -6 hours 30 minutes；Best, Contact Temperature is 100-170 DEG C, and time of contact is 30 minutes -4
Hour.By Contact Temperature and time of contact control within the above range, while quick removal binding agent is realized, avoid to dividing
The etching of son sieve crystal, and the compression strength of catalyst is maintained in optimal scope, obtain optimal binder free molecule
Sieve catalyst.
In above-mentioned technical proposal, the molecular sieve catalyst precursor and with molecular sieve catalyst precursor binding agent occur
At least one compound of chemical reaction contacts for the solution and organic amine of solute；Preferably, the organic amine includes being selected from second
At least one of amine, propylamine, butylamine, hexamethylene imine, piperidines, homopiperazine, ethylenediamine, hexamethylene diamine.Add simultaneously organic
Amine, effect are to protect molecular sieve crystal from above-mentioned solution etches, keep the integrality of molecular sieve crystal.
The preparation method of Adhesive-free Molecular Sieve catalyst of the present invention has the characteristics of universality is good, suitable for bag
Include but be not limited to MWW structures, MFI structure, CHA structure, FAU structures, * BEA structures, MOR structures, MTW structures, FER structures,
The molecular sieve of TON structures or SFE structures.
In above-mentioned technical proposal, MWW structure molecular screens include MCM-22, MCM-56, MCM-49, MCM-36, ITQ-2,
IEZ-MWW, UZM-8, SSZ-25, PSH-3, ERB-1, SCM-1, SCM-2, SCM-6, SRZ-21, EMM-10, EMM-12, EMM-
All molecular sieves including 13, SSZ-70, ECNU-7, MIT-1；MFI structure molecular sieve includes ZSM-5 molecular sieve；CHA structure point
Son sieve includes SSZ-13, SAPO-34 molecular sieve；FAU structure molecular screens include X, Y molecular sieve；* BEA structure molecular screens include
Beta molecular sieves；MOR structure molecular screens include mercerising molecular sieve；MTW structure molecular screens include ZSM-12 molecular sieves；FER structures
Molecular sieve includes ferrierite, ZSM-35 molecular sieve；TON structure molecular screens include ZSM-22 molecular sieves；SFE structure molecular screen bags
Include SSZ-48 molecular sieves.The present invention also provides a kind of nothing obtained according to the preparation method of above-mentioned Adhesive-free Molecular Sieve catalyst
Binding agent molecular sieve catalyst.
In the Adhesive-free Molecular Sieve catalyst, the content of binding agent is less than 3 weight %, preferably smaller than 2 weight %, more
Preferably smaller than 1 weight %.
The compression strength of the Adhesive-free Molecular Sieve is 60~120N/cm, and preferably compression strength is 65~100N/cm,
More preferably compression strength is 65~99N/cm, and more preferably compression strength is 81~99N/cm.
The present invention also provides the Adhesive-free Molecular Sieve synthesized according to the preparation method of above-mentioned Adhesive-free Molecular Sieve and is catalyzed
Application of the agent in organic molecule conversion aspect.
Non-binder MCM-22 molecular sieve catalyst and binder free Beta molecular sieve catalysts provided by the invention, in benzene
It is good with catalytic performance in preparing ethylbenzene by liquid phase alkylation of ethylene, the reaction of benzene alkylation with propylene preparing isopropylbenzene, alkylation can be used as
Catalyst is applied in benzene and preparing ethylbenzene by liquid phase alkylation of ethylene, the reaction of benzene alkylation with propylene preparing isopropylbenzene.
Adhesiveless ZSM-5 molecular sieve catalyst provided by the invention, in benzene and pure ethylene, benzene and dilute ethene, benzene and second
Catalytic performance is good in the reaction of alcohol producing ethyl benzene through alkylation in gas phase, can be used as alkylation catalyst be applied to benzene and pure ethylene, benzene with
In dilute ethene, benzene and the reaction of ethanol producing ethyl benzene through alkylation in gas phase.
Binder free Y molecular sieve catalyst provided by the invention, reacted in benzene and more ethylbenzene transalkylation reaction ethylbenzene
Middle catalytic performance is good, and alkylation catalyst can be used as to be applied in benzene and the reaction of more ethylbenzene transalkylation ethylbenzene ethylbenzene.
Binder free Cu-SSZ-13 molecular sieve catalysts provided by the invention, nitrogen oxides in exhaust gas from diesel vehicle
Catalytic performance is good in selective catalytic reduction process, the conversion of nitrogen oxides that can be applied to as catalyst in exhaust gas from diesel vehicle
In reaction.
For in the organic matter conversion process that is carried out in fixed bed reactors, it is necessary to which catalyst has certain pressure resistance
Degree is (more than 60N/cm), in order to avoid catalyst efflorescence, and then cause catalyst loss and bed pressure drop increase.But catalyst
Compression strength is not the higher the better, when the compression strength of catalyst is more than 120N/cm, such as 130N/cm, catalyst now
Catalytic performance significantly lower than compression strength less than compression strength be 120N/cm catalyst.Thus, for benzene and ethene and benzene
It should be controlled in 60~120N/cm with the compression strength of propylene liquid-phase alkylation preparing ethylbenzene by reaction, the molecular sieve catalyst of isopropylbenzene
Between, preferably compression strength is 65~100N/cm, and more preferably compression strength is 65~99N/cm, and more preferably compression strength is 81
~99N/cm.
In order to obtain the Adhesive-free Molecular Sieve catalyst of such compression strength, the present invention is using to molecular sieve containing binding agent
Catalyst carries out the method for post-processing selectively removing binding agent, prepares Adhesive-free Molecular Sieve catalyst, the method universality
Good, simple to operate, low for equipment requirements, the time is fast.In the absence of preparing binder free using secondary crystallization method in the prior art
Molecular sieve catalyst turns the problem of brilliant incomplete, the time is long and cumbersome.Using technical scheme, within 12 hours
The fast eliminating of binding agent can be achieved, the compression strength of gained catalyst is 60~120N/cm, and binding agent removing is thorough,
The content of binding agent is less than 3 weight % in product, achieves preferable technique effect.
Heretofore described Adhesive-free Molecular Sieve, the content of contained thing phase and each thing phase is tested by XRD.It is logical
Over-scan the removing situation of electron microscopic observation binding agent, and the pattern of molecular sieve.Catalyst containing binding agent is post-processed
The content of binding agent in obtained catalyst is true by the content of binding agent in XRD things mutually quantitative and stereoscan photograph
It is fixed.The method of molecular sieve silica alumina ratio chemical analysis determines.After the compression strength of molecular sieve uses pressure testing machine to roasting
Catalyst is tested, and method of testing is：The catalyst granules that length L is 0.4~0.6 centimetre is chosen, catalyst granules is horizontal
To being placed on test platform, gradually increase pressure to catalyst and be crushed, instrument records when catalyst is crushed automatically to be applied
Pressure F (newton, N), F and L ratio (F/L) are the compression strength of single catalyst.Test the resistance to compression of 10 catalyst
The compression strength that its average value is the catalyst is taken after intensity.
Brief description of the drawings
Fig. 1 is【Embodiment 1】The XRD spectra of the binder free MCM-22 molecular sieves of preparation.It can be seen that and spread out from its spectrogram
Penetrate peak and the characteristic diffraction peak of MCM-22 molecular sieves coincide.
Fig. 2 is【Embodiment 3】The XRD spectra of the binder free Beta molecular sieve catalysts of preparation.Can from its spectrogram
Go out, diffraction maximum and the characteristic diffraction peak of Beta molecular sieves coincide.
Fig. 3 is【Embodiment 4】The XRD spectra of the adhesiveless ZSM-5 molecular sieve catalyst of preparation.Can from its spectrogram
Go out, the characteristic diffraction peak of diffraction maximum and ZSM-5 molecular sieve coincide.
Fig. 4 is【Embodiment 5】The XRD spectra of the binder free Y molecular sieve catalyst of preparation.It can be seen that from its spectrogram
The characteristic diffraction peak of diffraction maximum and Y molecular sieve coincide.
Embodiment
【Embodiment 1】
A) synthesis (synthesis state molecular sieve) of molecular sieve：By sodium aluminate (Al2O343.0 weight %, Na2The weights of O 35.0
Measure %) 13.2 grams, 2.1 grams of sodium hydroxide, 366.0 grams of water, the hexamethylene imine aqueous solution (weight of hexamethylene imine 80.0
Measure %) 103.3 grams, Ludox (SiO240.0 weight %) 250.0 grams it is well mixed, the material proportion for obtaining reactant mixture (rubs
That ratio) be：
SiO2/Al2O3=30
NaOH/SiO2=0.12
Hexamethylene imine/SiO2=0.5
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 molecular sieve of synthesis state.The weight-loss ratio of test synthesis state molecular sieve is 16.4 weight %, is surveyed using ICP
The SiO of molecular sieve after must being calcined2/Al2O3Mol ratio be 29.1.
B) preparation of molecular sieve catalyst precursor：By above-mentioned 41.866 grams of synthesis state molecular sieve, alkaline silica sol (SiO2
40.0 weight %) 37.5 grams, 0.5616 gram of sesbania powder, aqueous solution of nitric acid (5 mass %) it is well mixed, prepared by extruded moulding
The strip molecular sieve catalyst precursor that molecular sieve content is 70 weight %, cross section is bunge bedstraw herb.
C) obtained molecular sieve catalyst precursor in step b) is contacted 3 hours with sodium hydrate aqueous solution at 150 DEG C, hydrogen
The mass ratio of aqueous solution of sodium oxide and molecular sieve catalyst precursor is 30：1, the mass fraction of sodium hydrate aqueous solution is 0.4%,
Solid product is separated, dried, molecular sieve catalyst is calcined 5 hours to obtain under 550 DEG C of air atmospheres by reaction after terminating.
The XRD spectra of product is as shown in Figure 1.The content of molecular sieve is up to 99.1 weight %, compression strength 76N/ in product
cm。
In the present embodiment, binding agent is made with alkaline silica sol, removed using sodium hydroxide in molded molecular sieve catalyst
Binding agent, sodium hydroxide reacts with amorphous silica therein (binding agent in molded molecular sieve catalyst), by its turn
The sodium metasilicate for being dissolved in water is turned to, so as to which the binding agent realized in molecular sieve catalyst efficiently and rapidly removes.
【Embodiment 2】
Together【Embodiment 1】, simply will 41.866 grams of synthesis state molecular sieve, alkaline silica sol (SiO in step b)240.0 weights
Measure %) 87.5 grams, 1.05 grams of sesbania powder, aqueous solution of nitric acid (5 mass %) it is well mixed, molecular sieve is prepared by extruded moulding and contained
Measure as 50 weight %, the strip molecular sieve catalyst precursor that cross section is bunge bedstraw herb.
C) obtained molecular sieve catalyst precursor in step b) is contacted 4 hours with sodium hydrate aqueous solution at 150 DEG C, hydrogen
The mass ratio of aqueous solution of sodium oxide and molecular sieve catalyst precursor is 25：1, the mass fraction of sodium hydrate aqueous solution is 0.6%,
Solid product is separated, dried, molecular sieve catalyst is calcined 5 hours to obtain under 550 DEG C of air atmospheres by reaction after terminating.
The XRD spectra of product is similar to Fig. 1.The content of molecular sieve is up to 98.2 weight %, compression strength 68N/ in product
cm。
【Embodiment 3】
A) synthesis (synthesis state Beta molecular sieves) of Beta molecular sieves：Using alkaline silica sol, Patent alum, four
Ethyl ammonium hydroxide (TEAOH) and water are synthesis material, are 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 3 days.Mistake after crystallization terminates
Filter, wash, being dried to obtain the Beta molecular sieves of synthesis state.The weight-loss ratio of test synthesis state Beta molecular sieves is 16.4 weight %.
B) preparation of Beta molecular sieve catalysts precursor：Above-mentioned 41.866 grams of synthesis state Beta molecular sieves, alkaline silicon is molten
Glue (SiO240.0 weight %) 37.5 grams, 0.5616 gram of sesbania powder, aqueous solution of nitric acid (5 mass %) it is well mixed, pass through extrusion
Shaping prepares the strip Beta molecular sieve catalyst precursors that Beta molecular sieve contents are 70 weight %, cross section is bunge bedstraw herb.
C) that obtained Beta molecular sieve catalysts precursor in step b) is contacted into 3 at 150 DEG C with sodium hydrate aqueous solution is small
When, the mass ratio of sodium hydrate aqueous solution and Beta molecular sieve catalyst precursors is 30：1, the quality point of sodium hydrate aqueous solution
Number is 0.4%, and solid product is separated, dried, Beta molecules are calcined 5 hours to obtain under 550 DEG C of air atmospheres by reaction after terminating
Sieve catalyst.
The XRD spectra of product is as shown in Figure 2.The content of molecular sieve is up to 99.1 weight %, compression strength 76N/ in product
cm。
In the present embodiment, binding agent is made with alkaline silica sol, shaping Beta molecular sieve catalysts are removed using sodium hydroxide
In binding agent, sodium hydroxide and amorphous silica therein (binding agent in molecular sieve catalyst) react, by its turn
The sodium metasilicate for being dissolved in water is turned to, so as to realize that the binding agent in Beta molecular sieve catalysts efficiently and rapidly removes.
【Embodiment 4】
A) synthesis (synthesis state ZSM-5 molecular sieve) of ZSM-5 molecular sieve：Using alkaline silica sol, Patent alum,
TPAOH (TPAOH) and water are synthesis material, are according to material proportion (mol ratio) by above-mentioned raw materials：
SiO2/Al2O3=180
TPAOH/SiO2=0.22
H2O/SiO2=18
After well mixed, it is fitted into stainless steel cauldron, under agitation in 150 DEG C of crystallization 3 days.Mistake after crystallization terminates
Filter, wash, being dried to obtain the ZSM-5 molecular sieve of synthesis state.The weight-loss ratio of test synthesis state ZSM-5 molecular sieve is 16.4 weights
Measure %.
B) preparation of ZSM-5 molecular sieve catalyst precarsor：By above-mentioned 41.866 grams of synthesis state ZSM-5 molecular sieve, alkaline silicon
Colloidal sol (SiO240.0 weight %) 37.5 grams, 0.5616 gram of sesbania powder, aqueous solution of nitric acid (5 mass %) it is well mixed, by squeezing
Before bar shaping prepares the strip ZSM-5 molecular sieve catalyst that ZSM-5 molecular sieve content is 70 weight %, cross section is bunge bedstraw herb
Body.
C) that obtained ZSM-5 molecular sieve catalyst precarsor in step b) is contacted into 3 at 150 DEG C with sodium hydrate aqueous solution is small
When, the mass ratio of sodium hydrate aqueous solution and ZSM-5 molecular sieve catalyst precarsor is 30：1, the quality point of sodium hydrate aqueous solution
Number is 0.4%, and solid product is separated, dried, ZSM-5 molecules are calcined 5 hours to obtain under 550 DEG C of air atmospheres by reaction after terminating
Sieve catalyst.
The XRD spectra of product is as shown in Figure 3.The content of molecular sieve is up to 99.1 weight %, compression strength 76N/ in product
cm。
【Embodiment 5】
A) synthesis (synthesis state Y molecular sieve) of Y molecular sieve：Using waterglass, Patent alum, sodium hydroxide and water
For synthesis material, it is according to material proportion (mol ratio) by above-mentioned raw materials：
SiO2/Al2O3=8
NaOH/SiO2=0.5
H2O/SiO2=18
After well mixed, it is fitted into stainless steel cauldron, under agitation in 100 DEG C of crystallization 24 hours.Crystallization terminates
The Y molecular sieve of synthesis state is filtered, washed, being dried to obtain afterwards.The weight-loss ratio of test synthesis state Y molecular sieve is 8.2 weight %.
B) preparation of Y molecular sieve catalyst precarsor：By above-mentioned 38.126 grams of synthesis state Y molecular sieve, alkaline silica sol (SiO2
40.0 weight %) 37.5 grams, 0.5616 gram of sesbania powder, aqueous solution of nitric acid (5 mass %) it is well mixed, prepared by extruded moulding
The strip Y molecular sieve catalyst precarsor that Y molecular sieve content is 70 weight %, cross section is bunge bedstraw herb.
C) obtained Y molecular sieve catalyst precarsor in step b) is contacted 3 hours with sodium hydrate aqueous solution at 150 DEG C,
The mass ratio of sodium hydrate aqueous solution and Y molecular sieve catalyst precarsor is 30：1, the mass fraction of sodium hydrate aqueous solution is
0.4%, solid product is separated, dried, is calcined under 550 DEG C of air atmospheres 5 hours and to obtain Y molecular sieve catalysis by reaction after terminating
Agent.
The XRD spectra of product is as shown in Figure 4.The content of molecular sieve is up to 99.1 weight %, compression strength 76N/ in product
cm。
In the present embodiment, binding agent is made with alkaline silica sol, removed using sodium hydroxide in shaping Y molecular sieve catalyst
Binding agent, sodium hydroxide react with amorphous silica therein (binding agent in molecular sieve catalyst), are translated into
The sodium metasilicate of water is dissolved in, so as to realize that the binding agent in Y molecular sieve catalyst efficiently and rapidly removes.
【Comparative example 1】
Together【Embodiment 1】, simply by 3.94 grams of sodium aluminate (Al2O343.0 weight %, Na2The weight % of O 35.0), 244 grams
Water, 15 grams of hexamethylene imine aqueous solution (the weight % of hexamethylene imine 80.0) are well mixed, then are mixed with molecular sieve precursor,
Gained mixture is placed in 150 DEG C of crystallization 40 hours, control binding agent alkaline silica sol (SiO240.0 weight %), silicon source (for
0), silica alumina ratio SiO total in silicon source sodium aluminate2/Al2O3=15.Crystallization is filtered after terminating, washs, dried, then at 550 DEG C
Product Adhesive-free Molecular Sieve is calcined 5 hours to obtain in air.The content of molecular sieve is up to 90.5 weight %, compression strength in product
101N/cm。
【Comparative example 2】
Together【Embodiment 1】, simply by 0.495 gram of sodium aluminate (Al2O343.0 weight %, Na2The weight % of O 35.0), 244
Gram water, 1.02 grams of NaOH (96 weight %), the 15 grams of hexamethylene imine aqueous solution (the weight % of hexamethylene imine 80.0) mixing
Uniformly, then with molecular sieve precursor mix, gained mixture is placed in 150 DEG C of crystallization 40 hours, controls binding agent alkaline silica sol
(SiO240.0 weight %), silicon source (for 0), silica alumina ratio SiO total in silicon source sodium aluminate2/Al2O3=120.Crystallization terminates
Filter, wash, dry afterwards, then product Adhesive-free Molecular Sieve is calcined 5 hours to obtain in 550 DEG C of air.Molecular sieve in product
Content is 83.8 weight %, compression strength 43N/cm.
【Comparative example 3】
Method according to document CN104671253A prepares non-binder MCM-22 molecular sieve catalyst：By SiO2/Al2O3
60 grams of=20 MCM-22 molecular sieves and alkaline silica sol (SiO240.0 weight %) 40 grams, 16 grams of aluminum sulfate, 1 mol/L hydrogen
Sodium hydroxide solution 10mL is well mixed, extruded moulding, after 80 DEG C of drying 3h, is placed in inner bag bottom and is contained hexamethylene imine and water weight
Amount is than being 1:In the 200mL of 1 40 grams of mixed solution autoclave, 165 DEG C of crystallization 80h take out, after 120 drying 3h, at 400 DEG C
2h is calcined, 550 DEG C of roasting 3h obtain MCM-22 molecular sieve catalysts.
The content of molecular sieve is 98.5 weight %, compression strength 150N/cm in product.
【Embodiment 6】
Will【Embodiment 1】In molecular sieve catalyst be used for continuous fixed bed benzene and ethylene liquid phase alkylation and react.Reaction
Before, first pass through ammonium exchange and catalyst is converted into Hydrogen.Alkylation reaction condition is：200 DEG C, pressure 3.5MPa of temperature, benzene/alkene
Charge proportion 3, Ethylene mass air speed 9h-1, after reaction is carried out continuously 5h, conversion of ethylene 65.3%.
【Comparative example 4】
Will【Comparative example 3】Middle gained catalyst is used for continuous fixed bed benzene and reacted with ethylene liquid phase alkylation.Before reaction, first
Exchanged by ammonium and catalyst is converted into Hydrogen.Alkylation reaction condition is：200 DEG C, pressure 3.5MPa of temperature, benzene/alkene charging
Ratio 3, Ethylene mass air speed 9h-1, after reaction is carried out continuously 5h, conversion of ethylene is only 45.3%.
【Embodiment 7】
Will【Embodiment 4】In ZSM-5 molecular sieve catalyst be used for continuous fixed bed benzene and pure ethylene vapor-phase alkylation it is anti-
Should.Before reaction, first pass through ammonium exchange and catalyst is converted into Hydrogen.Alkylation reaction condition is：380 DEG C of temperature, pressure
0.1MPa, benzene/alkene charge proportion 4, Ethylene mass air speed 3h-1, after reaction is carried out continuously 2h, conversion of ethylene 47.6%.
【Embodiment 8】
Will【Embodiment 5】In Y molecular sieve catalyst be used for continuous fixed bed benzene and diethylbenzene transalkylation ethylbenzene it is anti-
Should.Before reaction, first pass through ammonium exchange and catalyst is converted into Hydrogen.Alkylation reaction condition is：165 DEG C of temperature, pressure
The mass ratio of 3.5MPa, benzene and diethylbenzene is 2, total air speed 3.5h-1, after reaction is carried out continuously 3h, diethylbenzene conversion ratio is
75.6%.
Claims (19)
1. a kind of preparation method of Adhesive-free Molecular Sieve catalyst, comprises the following steps：By molecular sieve catalyst precursor and with
At least one compound that binding agent in the molecular sieve catalyst precursor chemically reacts contacts for the solution of solute, it
Solid product is separated to, dried, is calcined and to obtain molecular sieve catalyst afterwards.
2. the preparation method of Adhesive-free Molecular Sieve catalyst according to claim 1, it is characterised in that described and molecule
At least one compound that binding agent in sieve catalyst precursor chemically reacts includes the aqueous solution of acid for the solution of solute
Or the aqueous solution of alkali.
3. the preparation method of Adhesive-free Molecular Sieve catalyst according to claim 1, it is characterised in that described and molecule
At least one compound that binding agent in sieve catalyst precursor chemically reacts is divided for the quality of solute in the solution of solute
Number is 0.001%~5%.
4. the preparation method of Adhesive-free Molecular Sieve catalyst according to claim 1, it is characterised in that described and molecule
At least one compound that binding agent in sieve catalyst precursor chemically reacts is the solution and molecular sieve catalyst of solute
The mass ratio of precursor is 5~100：1.
5. the preparation method of Adhesive-free Molecular Sieve catalyst according to claim 1, it is characterised in that the contact temperature
Spend for not higher than 240 DEG C, the time of contact is -2 days 10 minutes.
6. the preparation method of Adhesive-free Molecular Sieve catalyst according to claim 1, it is characterised in that after roasting
The weight meter of molecular sieve catalyst precursor, the content of the molecular sieve in molecular sieve catalyst precursor is 40-90 weight %.
7. the preparation method of Adhesive-free Molecular Sieve catalyst according to claim 1, it is characterised in that the molecular sieve
Catalyst precarsor and at least one compound to be chemically reacted with the binding agent in molecular sieve catalyst precursor are solute
Solution and organic amine contact.
8. the preparation method of Adhesive-free Molecular Sieve catalyst according to claim 7, it is characterised in that the organic amine
Including selected from least one of ethamine, propylamine, butylamine, hexamethylene imine, piperidines, homopiperazine, ethylenediamine, hexamethylene diamine.
9. the preparation method of Adhesive-free Molecular Sieve according to claim 1, it is characterised in that the Contact Temperature is
100 DEG C~170 DEG C, time of contact is 30 minutes~4 hours；Chemistry occurs for the binding agent with molecular sieve catalyst precursor
Reaction at least one compound for solute solution include inorganic acid, organic acid, quaternary ammonium base, with alkali metal or alkaline earth gold
Belong to the aqueous solution of the element for the alkali of cation；The binding agent with molecular sieve catalyst precursor chemically reacts at least
A kind of compound be solute solution in the mass fraction of solute be 0.05%~1%；In described and molecular sieve catalyst precursor
At least one compound for chemically reacting of binding agent be that the mass ratio of solution and molecular sieve catalyst precursor of solute is
10~30：1.
10. the preparation method of Adhesive-free Molecular Sieve according to claim 9, it is characterised in that the inorganic acid includes
Nitric acid, hydrochloric acid, phosphoric acid or sulfuric acid, the organic acid include formic acid, acetic acid, propionic acid, acrylic acid or ethanedioic acid, the quaternary ammonium base bag
Include TMAH, tetraethyl ammonium hydroxide, TPAOH, TBAH, N, N, N- front three funds
Firm alkyl ammonium hydroxide or dimethyl diethyl ammonium hydroxide, it is described using alkali metal or alkali earth metal as cation
Alkali includes NaOH or KOH.
11. the preparation method of Adhesive-free Molecular Sieve catalyst according to claim 1, it is characterised in that by that will close
Mix, be molded with binding agent into state molecular sieve, drying the acquisition molecular sieve catalyst precursor.
12. the preparation method of Adhesive-free Molecular Sieve catalyst according to claim 11, it is characterised in that the bonding
Agent is included selected from least one of Ludox, smoke silica gel, waterglass, silicon-containing compound, aluminum oxide, the silicon-containing compound
Formula be Y4-nSiXn, wherein, n=1~4, Y are alkyl, and X is hydrolyzable groups；With the molecular sieve catalyst precursor after roasting
Weight meter, the content of the molecular sieve in molecular sieve catalyst precursor is 60~85 weight %.
13. the preparation method of Adhesive-free Molecular Sieve catalyst according to claim 1, it is characterised in that the molecule
Sieve includes but is not limited to MWW structures, MFI structure, CHA structure, FAU structures, * BEA structures, MOR structures, MTW structures, FER knots
The molecular sieve of structure, TON structures or SFE structures.
14. the preparation method of Adhesive-free Molecular Sieve catalyst according to claim 1, it is characterised in that also include such as
Lower step：Obtained molecular sieve catalyst is contacted at least one solution or steam of the pH value not higher than 7, afterwards by solid
Product separation, dry, roasting.
15. the preparation method of Adhesive-free Molecular Sieve catalyst according to claim 14, it is characterised in that the pH value
At least one solution not higher than 7 includes the aqueous solution of ammonium salt, the sour aqueous solution, alkali salt or rare earth metal salt it is water-soluble
Liquid, the steam include water vapour.
16. the binder free point of the preparation method synthesis of any one of the claim 1~15 Adhesive-free Molecular Sieve catalyst
Sub- sieve catalyst.
17. Adhesive-free Molecular Sieve catalyst according to claim 16, it is characterised in that the Adhesive-free Molecular Sieve
In catalyst, the content of binding agent is less than 2 weight %.
18. Adhesive-free Molecular Sieve catalyst according to claim 16, it is characterised in that the Adhesive-free Molecular Sieve
The compression strength of catalyst be 60~120 newton/centimetre.
19. the Adhesive-free Molecular Sieve catalyst of claim 1~15 methods described synthesis is in organic molecule conversion aspect
Using.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610440415.XA CN107511168B (en) | 2016-06-18 | 2016-06-18 | Preparation method of binder-free molecular sieve catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610440415.XA CN107511168B (en) | 2016-06-18 | 2016-06-18 | Preparation method of binder-free molecular sieve catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107511168A true CN107511168A (en) | 2017-12-26 |
| CN107511168B CN107511168B (en) | 2021-03-30 |
Family
ID=60720805
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610440415.XA Active CN107511168B (en) | 2016-06-18 | 2016-06-18 | Preparation method of binder-free molecular sieve catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107511168B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110026151A (en) * | 2019-04-29 | 2019-07-19 | 中国地质科学院郑州矿产综合利用研究所 | Method for improving adsorption capacity and strength of binderless nalsx molecular sieve |
| CN114433191A (en) * | 2020-10-20 | 2022-05-06 | 中国石油化工股份有限公司 | Preparation method of binder-free molecular sieve catalyst |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0568566B1 (en) * | 1991-01-23 | 1995-03-29 | Exxon Chemical Patents Inc. | Process for producing substantially binder-free zeolite |
| CN102039150A (en) * | 2009-10-13 | 2011-05-04 | 中国石油化工股份有限公司 | Preparation method of binderless Y zeolite catalyst |
| CN102343286A (en) * | 2011-07-14 | 2012-02-08 | 上海复榆新材料科技有限公司 | Catalyst based on binder-free zeolite molecular sieves and preparation method thereof |
| CN104230633A (en) * | 2013-06-17 | 2014-12-24 | 中国石油化工股份有限公司 | Liquid phase alkyl transfer method |
| CN105566050A (en) * | 2014-10-13 | 2016-05-11 | 中国石油化工股份有限公司 | Method for producing ethylbenzene from ethylene and benzene |
-
2016
- 2016-06-18 CN CN201610440415.XA patent/CN107511168B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0568566B1 (en) * | 1991-01-23 | 1995-03-29 | Exxon Chemical Patents Inc. | Process for producing substantially binder-free zeolite |
| CN102039150A (en) * | 2009-10-13 | 2011-05-04 | 中国石油化工股份有限公司 | Preparation method of binderless Y zeolite catalyst |
| CN102343286A (en) * | 2011-07-14 | 2012-02-08 | 上海复榆新材料科技有限公司 | Catalyst based on binder-free zeolite molecular sieves and preparation method thereof |
| CN104230633A (en) * | 2013-06-17 | 2014-12-24 | 中国石油化工股份有限公司 | Liquid phase alkyl transfer method |
| CN105566050A (en) * | 2014-10-13 | 2016-05-11 | 中国石油化工股份有限公司 | Method for producing ethylbenzene from ethylene and benzene |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110026151A (en) * | 2019-04-29 | 2019-07-19 | 中国地质科学院郑州矿产综合利用研究所 | Method for improving adsorption capacity and strength of binderless nalsx molecular sieve |
| CN110026151B (en) * | 2019-04-29 | 2021-11-26 | 中国地质科学院郑州矿产综合利用研究所 | Method for improving adsorption capacity and strength of binderless nalsx molecular sieve |
| CN114433191A (en) * | 2020-10-20 | 2022-05-06 | 中国石油化工股份有限公司 | Preparation method of binder-free molecular sieve catalyst |
| CN114433191B (en) * | 2020-10-20 | 2023-08-29 | 中国石油化工股份有限公司 | Preparation method of binder-free molecular sieve catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107511168B (en) | 2021-03-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101489677B (en) | A mcm-22 family molecular sieve composition, its method of making, and use for hydrocarbon conversions | |
| CN104549452B (en) | Toluene and methanol alkylation catalyst and preparation method and application thereof | |
| CN105217651B (en) | Si-Al molecular sieve SCM 6, its preparation method and use | |
| CN107512729A (en) | The preparation method of the molecular sieve of binderless ZSM-5 5 | |
| CN101723401B (en) | ZSM-5/ZSM-5 core-shell type zeolite molecular sieve | |
| CN101205072B (en) | Method for synthesizing low silica-alumina ratio beta zeolite | |
| JP2016502487A (en) | Use of zeolitic materials in methods for producing zeolitic materials and in converting oxygen-containing materials to olefins | |
| CN107512726A (en) | The preparation method of binder free Beta molecular sieves | |
| CN108928830B (en) | Molecular sieve SCM-17, its synthesis method and use | |
| CN101585546B (en) | Composite zeolite molecular sieve preparing method containing Y and Beta zeolite structures | |
| CN106745051A (en) | A kind of preparation method of the molecular sieves of HZSM 5 | |
| CN107511169A (en) | The molecular sieve catalysts of ZSM 5, preparation method and application | |
| CN107511168A (en) | The preparation method of Adhesive-free Molecular Sieve catalyst | |
| CN108114739A (en) | Support type multi-stage porous HZSM-5 catalyst | |
| CN107512727A (en) | The preparation method of binder free MWW structure molecular screens | |
| CN107511163A (en) | Molecular sieve catalyst, preparation method and application | |
| CN105668580A (en) | Composite-structure molecular sieve and synthetic method thereof | |
| CN107511175B (en) | MWW structure molecular sieve catalyst, preparation method and application | |
| CN103693654B (en) | A method of synthesis IM-5 molecular sieves | |
| CN102861606B (en) | Double-micropore composite molecular sieve, preparation method of double-micropore composite molecular sieve and application of double-micropore composite molecular sieve | |
| CN107511165A (en) | The preparation method of binder free mercerising molecular sieve catalyst | |
| CN107511171A (en) | The preparation method of binder free Beta molecular sieve catalysts | |
| KR101648654B1 (en) | Catalysts for improved cumene production and method of making and using same | |
| CN107511170A (en) | The preparation method of the molecular sieve catalyst of binderless ZSM-5 5 | |
| CN106824261A (en) | Ni-SSZ-13 catalyst, preparation method and its usage |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 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 |