CN105314652B - A kind of preparation method of the molecular sieves of H types ZSM 5 - Google Patents
A kind of preparation method of the molecular sieves of H types ZSM 5 Download PDFInfo
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Abstract
The invention belongs to technical field of molecular sieve preparation, more particularly to a kind of preparation method of the molecular sieves of H types ZSM 5.First using Template-free method hydro-thermal method synthesis Na types ZSM 5, the molecular sieves of Na types ZSM 5 are exchanged for the molecular sieves of H types ZSM 5 by the batch (-type) tiny structure suction filtration method then exchanged using washing acid using inorganic acid as exchange reagent.The batch (-type) tiny structure suction filtration method that the washing acid that the present invention is provided is exchanged integrates separation, exchanges, washes, also eliminate traditional acid treatment tank, eliminate and dry and roasting process, it not only simplify production procedure, reduce equipment, energy consumption is reduced, problem of environmental pollution is solved, and close to industrial processes.Compared to traditional ammonium salt exchange method and belt vacuum filter exchange method, this method has easy, energy-conservation and efficient advantage, and with obvious industrial application value.
Description
Technical field
The invention belongs to technical field of molecular sieve preparation, more particularly to a kind of preparation method of H types ZSM-5 molecular sieve.
Background technology
Cyclohexene hydration belongs to acid catalyzed reaction, it is necessary to which the catalyst of highly acid, H type ZSM-5 molecular sieves are current industry
More catalyst is used in production, it, which has, prepares easy, performance stabilization, easily separates, can be recycled for multiple times with reaction solution
Etc. clear advantage, commercial Application relatively succeeds.
The preparation of H type ZSM-5 molecular sieves is HZSM-5 by ion exchange typically by the Na types ZSM-5 molecular sieve of synthesis
Molecular sieve.The exchange of traditional Na types ZSM-5 molecular sieve uses ammonium salt exchange method.Ammonium salt therein includes ammonium nitrate, chlorine
Change ammonium, ammonium sulfate, ammonium hydroxide and ammonium acetate etc., and exchange the most classical with ammonium nitrate.But ammonium salt exchange after also need to through
Cross washing, dry and roasting could obtain H type ZSM-5 molecular sieves, process is comparatively laborious and dry and roasting process needs to disappear
Substantial amounts of energy is consumed, the cost of industrialized production is added, can also cause problem of environmental pollution.Recent study persons gradually taste
The exchange method of pilot production inorganic acid, inorganic acid therein includes nitric acid, hydrochloric acid, phosphoric acid and sulfuric acid etc..Due to ZSM-5 molecular sieve
With good acid resistance, in certain acid concentration and crystal formation keeps complete substantially under certain time of contact, as long as equipment and exchange
Condition is suitable, and it is feasible that acid, which is exchanged,.
CN 101041442A disclose a kind of fine grain strong acid type molecular sieve and its synthetic method.Its exchange step be
In the presence of inorganic acid, completed within 1-5 hours in room temperature to 90 DEG C of ion exchanges, inorganic acid used is hydrochloric acid, nitric acid, phosphoric acid or
Sulfuric acid, concentration is 0.5-2.0mol/L.After the completion of exchange H type ZSM-5 molecular sieves are can obtain by washing and filtering with dry.Should
Although exchange method eliminates calcination stepses, simplifies production procedure, reduces energy consumption, but still use and carry out on differing devices
Filtering, acid are exchanged and washing unit operation, have the shortcomings that equipment is more, cumbersome.
CN103359760 discloses a kind of sodium form molecular sieve ion exchange method for removing sodium.The molecular sieve includes octahedral
Molecular sieve, beta-molecular sieve, mercerising molecular sieve, ZSM-5 Series Molecules sieve, Y type molecular sieve etc..This method is first exchanged with acid solution
Filter, then exchange removing sodium with ammonium ion and the rare earth ion aqueous solution.The exchange method is reaching equal removing sodium level and not broken substantially
The consumption of ammonium salt needed for exchanging can be reduced on the premise of bad element's sieve crystal structure, is exchanged even without ammonium salt, so as to reduce very
To elimination ammonia and nitrogen pollution.Sour exchange process employs three kinds of exchanged forms, and wherein the third sour exchanged form is in vacuum belt
Multistage exchange and filtering are carried out on filter.
CN1176019C discloses a kind of ammonium ion exchange method of Y type molecular sieve.The molecular sieve is that a friendship one roasts Y types
Molecular sieve, the rate of filtration of molecular sieve pulp is improved by adding the mixture of alkali or alkali and salt in molecular sieve pulp, from
And solve the problem of molecular sieve can not carry out ion exchange on band filter.Simultaneously employ intermittent negative pressure filter into
Row experiment, and it is either of equal value in process or in effect to demonstrate both.Although it uses intermittent negative pressure mistake
Filtering method, but the patent unavoidably will also be subjected to be calcined deamination process, extra increasing using ammonium salt as reagent, later stage is exchanged
Add energy consumption, and there are problems that ammonia emission.Na type ZSM-5 molecular sieves are swapped using inorganic acid, its process is relative
Simplify, eliminate calcination stepses, not only reduce energy expenditure, and solve the emission problem of ammonia in roasting process.
Industrial molecular sieve inorganic acid, which is exchanged, has autoclave to exchange and band filter exchange two ways.Most of acid are exchanged
Process is exchanged using autoclave, i.e., acid exchange, two steps of separation are repeated multiple times under condition of normal pressure, and preparation process is still cumbersome, and production is automatic
Change degree is low, it is difficult to form serialization industrial manufacture process.Another exchanged form is exchanged using vacuum band-type filter machine, should
Exchange method can not only realize continuous production, and automaticity is high, can collect separation of solid and liquid, exchange, washes, filtering in one
Body, efficiency high.But the sour exchange method equipment of vacuum band-type filter machine is more complicated, invest larger, control parameter is more, does not allow
Amplification is easily realized, and molecular screen primary powder loss is higher.
The content of the invention
It is an object of the invention to provide a kind of preparation method of H types ZSM-5 molecular sieve, the interval exchanged using washing-acid
Formula negative pressure filtration method carries out inorganic acid exchange to Na types ZSM-5 molecular sieve.The exchange method molecular screen primary powder consumption and useless
Water discharge capacity greatly reduces, and has equivalent effect with vacuum band-type filter machine on exchange process and exchange result.
In order to solve the above technical problems, the technical solution adopted by the present invention is as follows：
A kind of preparation method of H types ZSM-5 molecular sieve, first prepares Na type ZSM-5 molecular sieve slurries, then using inorganic acid as
Exchange reagent, the batch (-type) tiny structure suction filtration exchanged using washing-acid to the separation of Na type ZSM-5 molecular sieves slurries progress suction filtration,
Acid is exchanged and washed, and Na type ZSM-5 molecular sieves directly are exchanged for into H type ZSM-5 molecular sieves without drying and being calcined.
Further, during described washing-acid exchanges batch (-type) tiny structure suction filtration, system pressure is controlled in -0.01MPa
To -0.1MPa.
Wherein, Stress control is whole, keeps pressure to maintain in suction filtration, exchange and washing whole process same
Level.
Described intermittent operation refers to that catalyst raw material is once all added, and is then taken out on same device
Filter, exchange and washing.It is the operation for being different from continous way, the operation of continous way is similar with industrial band filter process,
Catalyst raw material is continuously added to, and follow-up exchange reagent and deionized water is also what is be continuously added to, and whole process is in dynamic and connected
Continuous state.
Further, described Na type ZSM-5 molecular sieves concentration of slurry is 5-20wt%.
Further, described Na type ZSM-5 molecular sieves slurries can be prepared using Template-free method hydrothermal synthesis method, molten with silicon
Glue is silicon source, and aluminium hydroxide is silicon source, and the pH value of sodium hydroxide regulation precursor liquid is in 12-13, using ZSM-5 or S-1 as crystal seed,
70-90 DEG C of ageing 8-24h, 170-190 DEG C of crystallization 18-36h, obtain the former slurry liquid of Na types ZSM-5 molecular sieve；Wherein, crystal seed
Add the 1%-5% that quality is silica quality in system；Control raw material Na2O:SiO2：Al2O3:H2O mol ratio is (10-
13)：100：(2.5-3.5)：(2200-2900).It is of course also possible to use Na types ZSM-5 molecular sieve original powder adds water and prepares and obtain.
Further, carry out washing-acid exchange batch (-type) tiny structure suction filtration when use jacketed keep constant temperature
Filter, filtering material is aperture 1-5 microns of filter cloth or filter membrane.
Further, described inorganic acid is preferably nitric acid, hydrochloric acid, sulfuric acid or phosphoric acid.
Further, the temperature of described inorganic acid exchange process is 20-50 DEG C, inorganic acid volume/Na type ZSM-5 molecules
Sieve quality is 4-20mL/g, and the concentration of inorganic acid is 0.2-1.0mol/L.
Further, washing suction filtration to cake moisture is 30-50wt% after acid exchange terminates, and filtrate pH value is 6-7.
The application method uses the exchange method of batch (-type) tiny structure suction filtration, and inorganic acid is exchanged with uniform design
Condition is optimized, and exchanges the H type ZSM-5 molecular sieves obtained, and the sodium content in terms of sodium oxide molybdena is less than 0.1wt%, its silica
Mol ratio with aluminum oxide is 32-36, and particle size is 1-2 μm, and specific surface area is 360-460m2/g。
The inorganic acid exchange process of the present invention, which is eliminated, to be dried and roasting process, not only simplify exchange process, and
Solve the problem of too high exchange process energy consumption and environmental pollution.The exchange method of the batch (-type) tiny structure suction filtration used simultaneously,
Equipment simplifies, simple to operate, with easy, energy-conservation, efficient advantage.
In addition, it is that 30-50 wt%, filtrate pH value can close to after 7 that the molecular sieve after exchanging, which washes suction filtration to cake moisture,
Catalyst for hydration of olefines is directly used as, is such as used in the reaction of cyclohexene hydration cyclohexanol, higher cyclohexanol yield can be obtained.
The positive beneficial effect of the present invention
Simple synthetic method, the cost of Na type ZSM-5 molecular sieves are low, at the same the interval of Na type ZSM-5 molecular sieves decline it is negative
The sour exchange method of pressure suction filtration realize filtering-acid exchange-it is washing integrated, eliminate drying and roasting process, not only simplify
Production procedure, reduces energy consumption and former powder consumption, solves problem of environmental pollution, and be closer to industrial production mistake
Journey.Compared to traditional ammonium salt exchange method and belt vacuum filter exchange method, this method has easy, energy-conservation and efficient
Advantage, and with obvious industrial application value.
Embodiment
The present invention is described further for following example, but not thereby limiting the invention.
Embodiment 1
Using Ludox as silicon source, aluminium hydroxide is silicon source, and feed molar amount proportioning is 11.5Na2O : 100SiO2 :
3Al2O3 : 2750H2O, first adds appropriate water in 2L crystallizing kettle, then by the Al dissolved by heating in advance (OH)3With
NaOH mixed solution is added in kettle, and Ludox is added under conditions of at the uniform velocity stirring, and ZSM-5 is added afterwards and is used as crystal seed（Add
Measure as the 2.5% of silica quality, similarly hereinafter）, 80 DEG C of ageings 12h, 180 DEG C of crystallization 24h are cooled to room temperature, suction filtration, washing, do
It is dry to obtain the former powder of Na types ZSM-5 molecular sieve.
The above-mentioned Na types ZSM-5 molecular sieves prepared of 30g are taken in 500mL three-necked flasks, 400g deionized waters are added,
Mechanical agitation 4h is well mixed slurries.Slurries are poured into the Buchner funnel with chuck, taken out under the conditions of tiny structure
Filter, afterwards by the salpeter solution prepared in advance（Concentration is 0.5moL/L, and volume is 480mL, and temperature is maintained at 50 DEG C）Add
Exchanged to filter cake top suction filtration side acid, 300mL deionized waters are added after the completion of exchange, washing suction filtration to filtrate pH value is close to 7.It is whole
Individual procedures system vacuum degree control is in 0.040MPa to 0.045 MPa.
Obtained molecular sieve wet feed is denoted as A1, and wet feed water content is the particle that SEM is measured after 40wt%, 110 DEG C of dry 12h
In olive shape, grain diameter is 1-2 μm.
Comparative example 1
Using Ludox as silicon source, aluminium hydroxide is silicon source, and feed molar amount proportioning is 11.5Na2O : 100SiO2 :
3Al2O3 : 2750H2O, first adds appropriate water in 2L crystallizing kettle, then by the Al dissolved by heating in advance (OH)3With
NaOH mixed solution is added in kettle, and Ludox and crystal seed, 80 DEG C of ageing 12h, 180 DEG C of crystallization are added under conditions of at the uniform velocity stirring
24h, is cooled to room temperature, suction filtration, washes, is dried to obtain the former powder of Na types ZSM-5 molecular sieve.
The above-mentioned Na type ZSM-5 molecular sieves prepared of 30g are taken to pour into the ammonium nitrate solution that 300mL concentration is 1 moL/L
In, 3h is exchanged in 80 DEG C of constant temperature under reflux conditions, supernatant is outwelled in centrifugation.Repeat ammonium nitrate to exchange once, centrifuge, washing
It is 7 to filtrate pH value, by filter cake in 120 DEG C of dry 10h, 400 DEG C of roasting 6h.
Obtained molecular sieve siccative is denoted as B1.The particle that SEM Electronic Speculum is measured is in olive shape, and grain diameter is 1-2 μm.
Embodiment 2
Using Ludox as silicon source, aluminium hydroxide is silicon source, and feed molar amount proportioning is 11.5Na2O : 100SiO2 :
3Al2O3 : 2750H2O, first adds appropriate water in 2L crystallizing kettle, then by the Al dissolved by heating in advance (OH)3With
NaOH mixed solution is added in kettle, and Ludox and crystal seed, 80 DEG C of ageing 12h, 180 DEG C of crystallization are added under conditions of at the uniform velocity stirring
24h, is cooled to room temperature, suction filtration, washes, is dried to obtain the former powder of Na types ZSM-5 molecular sieve.
The above-mentioned Na types ZSM-5 molecular sieves prepared of 30g are taken in 500mL three-necked flasks, 400g deionized waters are added,
Mechanical agitation 4h is well mixed slurries.Slurries are poured into the Buchner funnel with chuck, first carried out under the conditions of tiny structure
Suction filtration, afterwards by the salpeter solution prepared in advance（Concentration is 0.2moL/L, and volume is 600mL, and temperature is maintained at 50 DEG C）
Enter the acid exchange of filter cake top suction filtration side, 300mL deionized waters are added after the completion of exchange and wash suction filtration to filtrate pH value close to 7.It is whole
Individual procedures system vacuum degree control is in 0.040MPa to 0.045 MPa.
Obtained molecular sieve wet feed is denoted as A2.Wet feed water content is 41wt%.
Embodiment 3
Using Ludox as silicon source, aluminium hydroxide is silicon source, and feed molar amount proportioning is 11.5Na2O : 100SiO2 :
3Al2O3 : 2750H2O, first adds appropriate water in 2L crystallizing kettle, then by the Al dissolved by heating in advance (OH)3With
NaOH mixed solution is added in kettle, and Ludox and crystal seed, 80 DEG C of ageing 12h, 180 DEG C of crystallization are added under conditions of at the uniform velocity stirring
24h, is cooled to room temperature, suction filtration, washes, is dried to obtain the former powder of Na types ZSM-5 molecular sieve.
The above-mentioned Na types ZSM-5 molecular sieves prepared of 30g are taken in 500mL three-necked flasks, about 400g deionizations are added
Water, mechanical agitation 4h is well mixed slurries.Slurries are poured into the Buchner funnel with chuck, it is advanced under the conditions of tiny structure
Row suction filtration, afterwards by the salpeter solution prepared in advance（Concentration is 0.2moL/L, and volume is 360mL, and temperature is maintained at 30 DEG C）
The acid exchange of filter cake top suction filtration side is poured into, 300mL deionized waters are added after the completion of exchange and wash suction filtration to filtrate pH value close to 7.
Whole process system vacuum is controlled in 0.040MPa to 0.045MP a.
Obtained molecular sieve wet feed is denoted as A3.Wet feed water content is 39wt%.
Embodiment 4
This example illustrates the preparation for the H type ZSM-5 molecular sieves that the present invention is provided
Using Ludox as silicon source, aluminium hydroxide is silicon source, and feed molar amount proportioning is 11.5Na2O : 100SiO2 :
3Al2O3 : 2750H2O, first adds appropriate water in 2L crystallizing kettle, then by the Al dissolved by heating in advance (OH)3With
NaOH mixed solution is added in kettle, and Ludox and crystal seed, 80 DEG C of ageing 12h, 180 DEG C of crystallization are added under conditions of at the uniform velocity stirring
24h, is cooled to room temperature, suction filtration, washes, is dried to obtain the former powder of Na types ZSM-5 molecular sieve.
The above-mentioned Na types ZSM-5 molecular sieves prepared of 30g are taken in 500mL three-necked flasks, about 400g deionizations are added
Water, mechanical agitation 4h is well mixed slurries.Slurries are poured into the Buchner funnel with chuck, it is advanced under the conditions of tiny structure
Row suction filtration, afterwards by the salpeter solution prepared in advance（Concentration is 0.2moL/L, and volume is 300mL, and temperature is maintained at 50 DEG C）
The acid exchange of filter cake top suction filtration side is poured into, 300mL deionized waters are added after the completion of exchange and wash suction filtration to filtrate pH value close to 7.
Whole process system vacuum is controlled in 0.040MPa to 0.045 MPa.
Obtained molecular sieve wet feed is denoted as A4.Wet feed water content is 40wt%.
Embodiment 5
This example illustrates the preparation for the H type ZSM-5 molecular sieves that the present invention is provided
Using Ludox as silicon source, aluminium hydroxide is silicon source, and feed molar amount proportioning is 11.5Na2O : 100SiO2 :
3Al2O3 : 2750H2O, first adds appropriate water in 2L crystallizing kettle, then by the Al dissolved by heating in advance (OH)3With
NaOH mixed solution is added in kettle, and Ludox and crystal seed, 80 DEG C of ageing 12h, 180 DEG C of crystallization are added under conditions of at the uniform velocity stirring
24h, is cooled to room temperature, suction filtration, washes, is dried to obtain the former powder of Na types ZSM-5 molecular sieve.
The above-mentioned Na types ZSM-5 molecular sieves prepared of 30g are taken in 500mL three-necked flasks, 400g deionized waters are added,
Mechanical agitation 4h is well mixed slurries.Slurries are poured into the Buchner funnel with chuck, first carried out under the conditions of tiny structure
Suction filtration, afterwards by the salpeter solution prepared in advance（Concentration is 0.5moL/L, and volume is 240mL, and temperature is maintained at 50 DEG C）
Enter the acid exchange of filter cake top suction filtration side, 300mL deionized waters washing suction filtration is added after the completion of exchange is to filtrate pH value close to 7
Can.Whole process system vacuum is controlled in 0.040MPa to 0.045 MPa.
Obtained molecular sieve wet feed is denoted as A5.Wet feed water content is 41wt%.
This example illustrates that the molecular sieve that the present invention is provided has preferable catalytic performance in cyclohexene hydration reaction.
Take 3g（Siccative）H types ZSM-5 molecular sieve made from embodiments above and comparative example each respectively with 30g deionizations
Water, 30mL cyclohexene are placed in 100mL autoclave, and 1h is reacted at 126 DEG C under 900rpm rotating speeds, and reaction is finished, and are cooled down,
The organic phase on upper strata is taken to carry out gas chromatographic analysis.Acquired results are listed in the table below 1.
Each catalyst cyclohexene hydration result of table 1
| Sequence number | Catalyst is numbered | Cyclohexanol yield/% |
| Embodiment 1 | A1 | 9.78 |
| Comparative example 1 | B1 | 9.34 |
| Embodiment 2 | A2 | 9.06 |
| Embodiment 3 | A3 | 8.44 |
| Embodiment 4 | A4 | 8.68 |
| Embodiment 5 | A5 | 8.51 |
Claims (6)
1. a kind of preparation method of H types ZSM-5 molecular sieve, it is characterised in that first prepare Na type ZSM-5 molecular sieve slurries, Na
Type ZSM-5 molecular sieve slurries are that, using Ludox as silicon source, aluminium hydroxide is silicon source, and the pH value of sodium hydroxide regulation precursor liquid exists
12-13, using ZSM-5 or S-1 as crystal seed, 70-90 DEG C of ageing 8-24h, 170-190 DEG C of crystallization 18-36h obtain ZSM-5 points of Na types
The former slurry liquid of son sieve；Wherein, the addition quality of crystal seed is the 1%-5% of silica quality in system；Control raw material Na2O:SiO2：
Al2O3:H2O mol ratio is (10-13)：100：(2.5-3.5)：(2200-2900), described Na types ZSM-5 molecular sieve slurry
Liquid concentration is 5-20wt%；
Then using inorganic acid as reagent is exchanged, the batch (-type) tiny structure suction filtration exchanged using washing-acid is to Na type ZSM-5 molecular sieves
Slurries carry out suction filtration separation, acid and exchange and wash, and Na type ZSM-5 molecular sieves directly are exchanged for into H types without dry and roasting
ZSM-5 molecular sieve.
2. the preparation method of H types ZSM-5 molecular sieve according to claim 1, it is characterised in that described washing-acid is handed over
Change during batch (-type) tiny structure suction filtration, system pressure control arrives -0.1MPa in -0.01MPa.
3. the preparation method of H types ZSM-5 molecular sieve according to claim 2, it is characterised in that-acid exchange is washed in progress
Batch (-type) tiny structure suction filtration when use the filter for keeping constant temperature of jacketed, filtering material is that aperture 1-5 is micro-
The filter cloth or filter membrane of rice.
4. the preparation method of H types ZSM-5 molecular sieve according to claim 1, it is characterised in that described inorganic acid is nitre
Acid, hydrochloric acid, sulfuric acid or phosphoric acid.
5. the preparation method of H types ZSM-5 molecular sieve according to claim 4, it is characterised in that described inorganic acid is exchanged
Process temperature is 20-50 DEG C, and inorganic acid volume/Na type ZSM-5 molecular sieves quality is 4-20mL/g, and inorganic acid concentration is 0.2-
1.0mol/L。
6. the preparation method of H types ZSM-5 molecular sieve according to claim 5, it is characterised in that acid exchange is washed after terminating
Suction filtration to cake moisture is 30-50wt%, and filtrate pH value is 6-7.
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|---|---|---|---|---|
| CN102079531A (en) * | 2009-11-27 | 2011-06-01 | 中国石油化工股份有限公司 | Method for reducing ammonium nitrogen dosage in process of producing molecular sieve |
| CN102989501A (en) * | 2012-12-11 | 2013-03-27 | 神华集团有限责任公司 | Preparation method of H-ZSM-5 molecular sieve based catalyst and prepared catalyst |
| CN103157507A (en) * | 2011-12-15 | 2013-06-19 | 中国石油天然气股份有限公司 | Heavy oil catalytic cracking catalyst and preparation method thereof |
| CN103848438A (en) * | 2014-03-06 | 2014-06-11 | 太原理工大学 | Modified ZSM-5 molecular sieve as well as modifying method and application thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102079531A (en) * | 2009-11-27 | 2011-06-01 | 中国石油化工股份有限公司 | Method for reducing ammonium nitrogen dosage in process of producing molecular sieve |
| CN103157507A (en) * | 2011-12-15 | 2013-06-19 | 中国石油天然气股份有限公司 | Heavy oil catalytic cracking catalyst and preparation method thereof |
| CN102989501A (en) * | 2012-12-11 | 2013-03-27 | 神华集团有限责任公司 | Preparation method of H-ZSM-5 molecular sieve based catalyst and prepared catalyst |
| CN103848438A (en) * | 2014-03-06 | 2014-06-11 | 太原理工大学 | Modified ZSM-5 molecular sieve as well as modifying method and application thereof |
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