CN109847787A - The rotational forming preparation method and applications of the microballoon total silicon molecule sieve catalyst of MFI topology containing trace rare-earth ion - Google Patents
The rotational forming preparation method and applications of the microballoon total silicon molecule sieve catalyst of MFI topology containing trace rare-earth ion Download PDFInfo
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Abstract
The present invention relates to silica zeolite fields, disclose a kind of rotational forming preparation method and applications of the microballoon total silicon molecule sieve catalyst of MFI topology containing trace rare-earth ion, preparation method includes: a, by the mixing of silicon source, rare earth ion source, organic formwork agent and water, obtains colloid admixture；B, colloid admixture is segmented hydrothermal crystallizing, and gained crystallization product is carried out film filtering and is washed, obtains the silica zeolite containing trace rare-earth ion after dry；C, silica zeolite is crushed, is mixed with binder, rotational forming is microballoon total silicon molecule sieve catalyst；D, it roasts, is contacted with the alkaline buffer solution of nitrogenous compound, wash, filter, dry finished product.The abrasion index of the catalyst is low, and the Technical Economy of new process can be improved in the vapor phase beckmann rearrangement reaction for carrying out cyclohexanone oxime in fluidized-bed process.
Description
Technical field
The present invention relates to silica zeolite field more particularly to a kind of MFI topologies containing trace rare-earth ion
The rotational forming preparation method and applications of microballoon total silicon molecule sieve catalyst.
Background technique
Silicalite-1 molecular sieve (- 1 molecular sieve of abbreviation total silicon) was in the E.M.Flanigen etc. by UCC company in 1978
It is successfully synthesized out for the first time, belongs to the last one member of " Pentasil " family.- 1 molecular sieve of total silicon is that one kind has
MFI topology without aluminum molecular screen, be to form a kind of simplest molecular sieve in ZSM-5 type structure molecular screen family,
Skeleton only contains silicon atom and oxygen atom, basic structural unit SiO4Tetrahedron.- 1 molecular sieve of total silicon possesses micropore abundant
Structure and regular uniform three-dimensional tubulus, have the crystal structure of determining type ZSM 5 molecular sieve, higher interior specific surface
Product, the performances such as good thermal stability, absorption and desorption ability.- 1 molecular sieve of total silicon can be used as chemical sensor, photoelectricity sound wave
The application material of device and membrane reactor.Gas-permeable membrane, pervaporation membrane, sensing are applied to especially as molecular screen membrane
Material membrane, optical material film etc..Therefore, -1 molecular sieve of total silicon is in fields such as film adsorbing separation, purification, catalysis materials
Development and application are just by the pay attention to day by day of people.
The synthetic method of -1 molecular sieve of total silicon generally uses traditional Organic Ingredients hydro-thermal method, and solid oxidation can be selected in silicon source
Silicon, silica solution, white carbon black, ethyl orthosilicate (abbreviation TEOS) etc., template mostly use tetrapropylammonium hydroxide (referred to as
TPAOH), low-carbon hydro carbons quaternary ammonium salt or both mixture, aminated compounds etc., the crystallization three days at a temperature of 170 DEG C.U.S.'s connection
The research groups such as conjunction carbide company (UCC), Sweden Stety and India P.Ratnasamy once carried out research in this respect.
- 1 molecular sieve of total silicon is mainly used in inorganic microporous investigation of materials field by them.
The silica zeolite of MFI structure disclosed in Japan Patent JP59164617 is to be with ethyl orthosilicate (TEOS)
Silicon source, tetrapropylammonium hydroxide are template preparation.In CATAL.REV.-SCI.ENG., 39 (4), 395~424 (1997)
In studies have shown that the total specific surface of silica zeolite BET with higher synthesized using ethyl orthosilicate as silicon source and outer surface
Product, can respectively reach 400 meters2/ gram and 15-30 meters2/ gram, and the selectivity of the conversion ratio of cyclohexanone oxime and caprolactam and outer
The increase of surface area is directly proportional.
Silica zeolite disclosed in Chinese patent CN00123576.1 and ZL00123577.x includes two kinds of synthesis sides
Method, method first is that: after mixing at room temperature with tetrapropylammonium hydroxide by ethyl orthosilicate, stir, hydrolyze, be warming up to 70-
75 DEG C, add water, by mixture hydrothermal crystallizing, then closed processes after mixing with organic base, needs to increase temperature in synthesis process
Catch up with alcohol.Method second is that ethyl orthosilicate is mixed at room temperature with tetrapropylammonium hydroxide, is stirred, after hydrolysis, Jia Shui plus
Ethyl alcohol, forming molar concentration is TPAOH/SiO2=0.05-0.5, EtOH/SiO2=4-30, H2O/SiO2The mixing of=2-100
Object；By mixture hydrothermal crystallizing；Product of roasting and organic base closed processes after mixing have been added in synthesis process big
Ethyl alcohol is measured, the cost of raw material is high, and COD discharge amount is big, and the molecular sieve solid content of synthesis reactor is low.
Silica zeolite disclosed in Chinese patent CN 102050464A, synthesis process include the following steps: (1) by positive silicon
Acetoacetic ester is mixed at room temperature with tetrapropylammonium hydroxide, is stirred, being fully hydrolyzed 3-5 hours, water supplement, forms molar concentration
For TPAOH/SiO2=0.05-0.5, EtOH/SiO2=4, H2O/SiO2The mixture of=5-100；(2) said mixture is existed
In closed reactor, 80-120 DEG C crystallization 0.5-10 days under self-generated pressure are washed out, filter, dry, 400-600 DEG C of roasting
1-10 hours.
ZL200910210326.6 discloses a kind of synthetic method of silica zeolite, which is with silicic acid second
Ester is silicon source, tetrapropylammonium hydroxide is alkali source and template, and gel mixture mole forms before Crystallization of Zeolite are as follows: SiO2:
0.05~0.5TPAOH:4EtOH:5~100H2O, 80~120 DEG C are made for crystallization 1~3 day.The obtained molecular sieve of this method
When preparing caprolactam for Cyclohexanone-Oxime Gas Phase Beckmann Rearrangement, there is very high cyclohexanone oxime conversion ratio and acyl in oneself
Amine selectivity.
Since silica zeolite is in extruded moulding, compression molding, or even molding etc. is rolled in the presence of very big difficulty, even if
After molding, the crushing strength of catalyst is very unsatisfactory (< 60N/cm or < 1kg/ particle), cannot achieve industrialization at all and answers
With.
Caprolactam is the primary raw material for producing polyamide fibre, industrial cord fabric thread and the big series of products of nylon engineering plastic three,
Its demand is more prosperous always.The caprolactam is generally obtained by the Beckmann rearrangement of cyclohexanone oxime.Currently, industrial
On generally use using the concentrated sulfuric acid or oleum as the liquid phase rearrangement technique of catalyst.The caprolactam of technique production accounts for generation
90% or so of boundary's caprolactam production total amount, but the process requirement consumes a large amount of sulfuric acid and ammonium hydroxide, general every production 1
For ton caprolactam by 1.3~1.8 tons of ammonium sulfate of by-product, production cost is higher.In addition the use of sulfuric acid will cause equipment corrosion and
The problems such as environmental pollution.
Cyclohexanone-Oxime Gas Phase Beckmann Rearrangement on solid acid catalyst is to realize caprolactam without the new of sulphur ammonium
Technique has the problems such as no equipment burn into non-environmental-pollution, and the separating-purifying of product will also greatly simplify, therefore without sulphur ammonium
Very big concern of the vapor phase beckmann rearrangement reaction technique by insider.
In order to develop be suitable for vapor phase beckmann rearrangement reaction solid acid catalyst, domestic and international researcher oneself to oxide
The catalyst such as (composite oxides), zeolite molecular sieve have carried out a large amount of research, the results showed that most of catalyst all have one
Fixed activity, but common disadvantage is that catalyst is easy inactivation, and catalyst life is short, cannot reach industrialized requirement.
Make to produce technique that is more economical, more meeting greenization requirement to be gas phase beckmann rearrangement method.Carry out cyclohexanone oxime
The method of gas phase beckmann rearrangement caprolactam does not use sulfuric acid and ammonium hydroxide, with no equipment burn into non-environmental-pollution and not
The advantages that by-product sulphur ammonium.As there are many solid acids of catalyst in vapor phase method Beckmann rearrangement, such as: British patent
One aluminium oxide catalyst of silica used in GB881,927；The solid phosphoric acid used in British patent GB881,956 is urged
Agent；The catalyst of the boronic acid containing used in British patent GB1,178,057；The height used in Chinese patent CN1269360A
Silicon/aluminium ratio MFI structural molecule sieve catalyst etc..Up to the present, fluidized-bed process is relatively suitble to gas phase beckmann rearrangement anti-
It answers, microballoon is suitable for the catalyst for making the technique.
Spray shaping is a kind of most common method for preparing microspherical catalyst, simple, practical, therefore is led by petrochemical industry
Domain is widely used.Spray shaping belongs to the spraying technical process combined with drying.The work that raw slurry is first passed through into atomizer
With the tiny misty liquid droplets of sprinkling poling, is then uniformly mixed by hot-air with misty liquid droplets, then quickly carry out heat exchange
With mass exchange make moisture evaporate to get particulate preparation.Such as microballoon.
Spray shaping is divided into pressure type, eccentric circle disc type, three kinds of air-flowing type, has process flow simple, convenient for production, raw
Production capacity power is strong, is easy the features such as adjusting control catalyst particle diameter, size distribution and moisture content.But the thermal efficiency of spray shaping
It is low, for sticky plaster pasty materials, pump difficulty of transportation, spray shaping after need to diluting, and meanwhile it is more demanding to gas-particle separation,
Equipment is huge.Since catalyst is by spray function, the intensity of microballoon is general.
It is proposed in European patent EP 576,295, in the case where not adding any binder, by being spray-dried molecule
Microballoon is made in sieve, is then heat-treated in water to improve the mechanical strength of microballoon, so that the microspherical catalyst can be used in
Cyclohexanone oxime is converted into the fluidized-bed reactor of caprolactam.Obviously, such intensity is not to be able to satisfy industrial application demand
's.
Disclosed in Chinese patent CN1256967A it is a kind of for cyclohexanone oxime be converted into caprolactam reaction, contain
The preparation method of MFI structural molecule sieve catalyst.The basic point of departure of this method is using acidic silica gel as binder, specifically
Method is: by the subparticle of siliceous oligomer made from alkoxyl silicone acidic hydrolysis and the MFI structure molecular sieve of pH≤5
Water or alcohol-aqueous dispersions mixing make emulsifying mixture, solidification, washing, roast obtained gel micro-ball.The catalyst is suitable for stream
Fluidized bed reactor.
It is binder preparation containing titanium-silicon molecular sieve catalyst that one kind is disclosed in United States Patent (USP) USP485985 using alkaline silica gel
Method.The alkaline silica gel is by tetraalkyl silicate, and preferably tetraalkyl orthosilicate is water-soluble in tetra-alkyl ammonium hydroxide
In liquid, room temperature to 200 DEG C hydrolyze 0.2~10 hour made from, pH >=10 of the alkaline silica gel.Obtained catalyst
For the microspherical catalyst suitable for fluidized-bed reactor.
That there are catalyst lifes is short for Cyclohexanone-Oxime Gas Phase Beckmann Rearrangement fixed bed or moving bed process, it is difficult to long week
Phase continuous operation, nitrogen oxime molar ratio is high, moves heat difficulty, and Technical Economy is poor.Fluidized-bed process is relatively suitble to cyclohexanone oxime gas phase
Beckmann rearrangement.
So far there is not yet the silica zeolite containing extremely trace rare-earth ion is rolled (rotation) molding
It is applied to related document, the patent of Cyclohexanone-Oxime Gas Phase Beckmann Rearrangement in turn for microspheroidal.
Summary of the invention
The microspheric MFI topology containing trace rare-earth ion that in order to solve the above-mentioned technical problems, the present invention provides a kind of
The rotational forming preparation method and applications of structure total silicon molecule sieve catalyst, the abrasion index of catalyst of the invention is low, uses
The Technical Economy of new process can be effectively improved in the vapor phase beckmann rearrangement reaction for carrying out cyclohexanone oxime in fluidized-bed process.
The specific technical proposal of the invention is: a kind of microballoon total silicon of the MFI topology containing trace rare-earth ion point
The rotational forming preparation method of sub- sieve catalyst, comprising the following steps:
A, silicon source, rare earth ion source, organic formwork agent and water are mixed, obtains colloid admixture；Wherein, the colloid admixture
Middle SiO2, organic formwork agent, water with molar ratio be 1: (0.05-0.50): (5-100)；In terms of silica, silicon source with it is dilute
The mass ratio of native ion is (10000-200000): 1.
B, the colloid admixture is first hydrothermal crystallizing 0.5-3 days at 50-60 DEG C, then the hydrothermal crystallizing at 80-120 DEG C
0.5-3 days, gained crystallization product is carried out film filtering and washed to pH value to be 8-10, is obtained after dry containing trace rare-earth ion
MFI topology silica zeolite.
C, it is 100~0000 mesh that the silica zeolite of the MFI topology by described containing trace rare-earth ion, which crushes, so
It is mixed afterwards with binder, is the microballoon for the MFI topology that granularity is 20~400 μm using rotational forming machine rotational forming
Total silicon molecule sieve catalyst；The rotary speed of rotational forming machine is 30-70rpm, and turntable inclination angle is 0-30 °.
D, the microballoon total silicon molecule sieve catalyst of MFI topology obtained in step c is roasted, after roasting
The microballoon total silicon molecule sieve catalyst of MFI topology contacted with the alkaline buffer solution of nitrogenous compound, then wash
It washs, filter, finished product after drying.
The complexity that different cations enter framework of molecular sieve is different, for example Si, Al etc. are relatively easy to enter molecular sieve
Skeleton, transition metal is more difficult to get access, and the difficulty of noble metal is bigger.And the atom of rare earth element, ionic radius are more than noble metal
Greatly, it is meant that it is more difficult to enter framework of molecular sieve than noble metal.The present invention is using specific segmentation, the skill of variable temperature crystallization
Art means solve the problems, such as that rare earth ion is difficult to enter framework of molecular sieve, so that extremely micro rare earth ion is able to enter
In -1 framework of molecular sieve of total silicon.The MFI topology silicon containing trace rare-earth ion has successfully been made in the whole world in the present invention for the first time
Molecular sieve.For rare earth compared with the elements such as other noble metals, cost is lower, particularly in China, the high situation of rare earth reserves
Under, cost advantage is more obvious.
Preferably, gained catalyst is on the basis of dry weight, including with 70~95wt% of dry basis containing micro-
Measure the silica zeolite of the MFI topology of rare earth ion and the binder of 5~30wt%；The partial size of the catalyst is
40~200 μm, abrasion index K is less than 5.
Preferably, the BET specific surface area of the silica zeolite of the MFI topology containing trace rare-earth ion is
400-500m2The weight ratio of silica and rare earth ion is (10000- in the silica zeolite of/g, MFI topology
200000)∶1。
Preferably, gained catalyst is on the basis of dry weight, including with the total silicon of 80~90wt% of dry basis
The binder of molecular sieve and 10~20wt%.
Preferably, the binder is silica solution, the sodium ions content of the silica solution is 10-500ppm, SiO2Contain
Amount is 20-45wt%.
Preferably, the rare earth ion is selected from Ce in step a3+、Ce4+、La3+At least one of；The rare earth from
Component is at least one of the nitrate containing the rare earth ion, chlorate, acetate and carbonate.
Preferably, the rare earth ion source is selected from La (NO3)3·6H2O、La(OAc)3·5H2O、LaCl3·7H2O、
La2(CO3)3·xH2O、Ce(NO3)3·6H2O、Ce(NO3)4·7H2O、Ce(OAc)3·5H2O、Ce(SO4)2·2H2O、
CeCl3·7H2At least one of O.
Preferably, the silicon source is selected from least one of silica gel, silica solution and organosilicon acid esters in step a；It is described
Organic formwork agent is selected from least one of fat amine compound, alcamine compound and quaternary amine alkaloid compound；Wherein, institute
The general formula for stating fat amine compound is R2(NH2)n, R2For the alkyl with 1-6 carbon atom, integer of the n between 1-3,
The general formula of the alcamine compound is (HOR3)mN, R3For the alkyl with 1-4 carbon atom, integer of the m between 1-3,
The alkyl quaternary amine alkali class compound has 1-4 carbon atom.
Preferably, the general formula of the organosilicon acid esters is (OR1)4Si, wherein R1For the alkyl of 1-4 carbon atom.
Methyl silicate and/or ethyl orthosilicate preferably, the organosilicon acid esters is positive；The organic formwork agent is alkane
Base quaternary amine alkaloid compound and/or fat amine compound；The alkyl quaternary amine alkali class compound is tetraethyl ammonium hydroxide
And/or tetrapropylammonium hydroxide；The fat amine compound is selected from ethamine, n-butylamine, n-propylamine, ethylenediamine and hexamethylene diamine
At least one of.
Preferably, the colloid admixture further includes low-carbon alcohols in step a, the low-carbon alcohols and SiO2Molar ratio
Be 1: (4-15), the low-carbon alcohols are ethyl alcohol.
Preferably, rotational forming is carried out in the case where addition has additive in step c, the additive is selected from field
Cyanines powder, graphite, active carbon, paraffin, stearic acid, glycerol, oxalic acid, tartaric acid, citric acid, starch, polyethylene glycol, polyethylene
Alcohol, polyethylene oxide, polypropylene amine, methyl cellulose, cellulose, polymeric alcohol, nitric acid, hydrochloric acid, acetic acid, formic acid, ammonium hydroxide, four
At least one of ammonium hydroxide, tetraethyl ammonium hydroxide and tetrapropylammonium hydroxide；The dosage of the additive is point
1~5wt% of son sieve dry weight.
Preferably, the alkaline buffer solution of the nitrogenous compound contains ammonium salt and alkali, the ammonium salt in step d
Content is 0.5-20wt%, and the content of the alkali is 5-30wt%, and the pH value of the alkaline buffer solution of the nitrogenous compound is
8.5-13.5。
Preferably, the ammonium salt is at least one of ammonium carbonate, ammonium fluoride, ammonium chloride, ammonium acetate and ammonium nitrate；Institute
Stating alkali is at least one of ammonium hydroxide, tetramethylammonium hydroxide, tetraethyl ammonium hydroxide and tetrapropylammonium hydroxide.
Preferably, the ammonium salt is ammonium acetate and/or ammonium nitrate；The alkali is ammonium hydroxide.
Preferably, the alkaline buffer of the molecular sieve and nitrogenous compound after the roasting in terms of butt is molten in step d
The weight ratio of liquid is 1: (5-15), the temperature of contact are 50-120 DEG C, and the pressure of contact is 0.5-5kg/cm2, the time of contact
It is 10-300 minutes, and determines whether that the alkaline buffer solution for being repeated several times nitrogenous compound post-processes depending on the performance of catalyst.
Preferably, in step d, the condition of the roasting are as follows: temperature is 200-600 DEG C, and the time is 1-20 hours.
The invention also discloses a kind of preparation methods of caprolactam, comprising: by cyclohexanone oxime in the presence of the solvent with
The contact of catalyst made from preceding method carries out vapor phase beckmann rearrangement reaction.
Preferably, the molar ratio of the solvent and cyclohexanone oxime is (2-10): 1；The solvent is the rouge selected from C1-C6
Fat alcohol, preferably methanol and/or ethyl alcohol.
Preferably, the vapor phase beckmann rearrangement reaction carries out in the presence of nitrogen, the nitrogen and cyclohexanone oxime
Molar ratio be (10-80): 1.
Preferably, carrying out the condition of the vapor phase beckmann rearrangement reaction are as follows: the weight space velocity of cyclohexanone oxime is 0.1-
20 hours-1, reaction temperature is 300-500 DEG C, reaction pressure 0.1-0.5MPa.
With water in molar ratio it is 1 by cyclohexanone oxime preferably, this method further includes: after (0.01-2.5) is mixed,
It is contacted in the presence of the solvent with the catalyst again and carries out vapor phase beckmann rearrangement reaction.
A small amount of water is added in cyclohexanone oxime, the service life of catalyst can be extended.
It is compared with the prior art, the beneficial effects of the present invention are: pole is added in silica zeolite synthesis process in the present invention
Its micro rare earth ion can effectively change the performance of silica zeolite, then pass through special strength rotational forming equipment
Silica zeolite is formed, the microballoon total silicon molecule of the MFI topology with higher-strength and wearability has been obtained
Sieve catalyst.In fluidized-bed reaction system, cyclohexanone oxime is carried out using microballoon total silicon molecule sieve catalyst disclosed by the invention
Vapor phase beckmann rearrangement reaction prepares caprolactam, is able to achieve caprolactam long period, continuous production, than existing total silicon molecule
Sieve catalyst has higher caprolactam overall selectivity and total recovery, and since by-product total amount declines, product separates energy
Consumption will also decline, and Technical Economy effectively improves.
Detailed description of the invention
Fig. 1 is that the microballoon silica zeolite containing the extremely MFI topology of trace rare-earth ion prepared by embodiment 1 is urged
The photo of agent.
Specific embodiment
The present invention will be further described with reference to the examples below.The BET of silica zeolite sample compares table in embodiment
Face, Extra specific surface area data are measured by U.S.'s Micromeritics ASAP-2400 type automatic absorbing instrument, test condition are as follows: N2Make
Adsorbate, adsorption temp are -196.15 DEG C (liquid nitrogen temperature), the constant temperature degassing 6h at 1.3Pa, 300 DEG C.Use Baird PS-
4 type ICP-AES plasma inductive coupling Atomic Emission Spectrometer AESs measure the rare earth ion content of sample, test condition are as follows: use
HF acid or aqua regia dissolution's solid molecular sieves or catalyst, make the silica volatility in sample, measure in aqueous solution.Catalyst
Size distribution be measured using the BT-9300S type laser fineness gage of Baite Instrument Co., Ltd., Dandong, test
Method is that wet process is tested, water as medium, sample concentration: 0.5%~2%, scanning speed is 2000 times/second.The pattern of catalyst
It takes pictures for general camera.Catalyst abrasion index K according to " petrochemical analysis method " (Yang Cuiding et al., Science Press,
Nineteen ninety) in RIPP29-90 method measured on wear index analyzer.
Total embodiment
A kind of rotational forming preparation side of the microballoon total silicon molecule sieve catalyst of the MFI topology containing trace rare-earth ion
Method, comprising the following steps:
A, silicon source, rare earth ion source, organic formwork agent and water are mixed, obtains colloid admixture；Wherein, the colloid admixture
Middle SiO2, organic formwork agent, water with molar ratio be 1: (0.05-0.50): (5-100)；In terms of silica, silicon source with it is dilute
The mass ratio of native ion is (10000-200000): 1.
B, the colloid admixture is first hydrothermal crystallizing 0.5-3 days at 50-60 DEG C, then the hydrothermal crystallizing at 80-120 DEG C
0.5-3 days, gained crystallization product is carried out film filtering and washed to pH value to be 8-10, is obtained after dry containing trace rare-earth ion
MFI topology silica zeolite.
C, it is 100~0000 mesh that the MFI topology silica zeolite by described containing trace rare-earth ion, which crushes, then
It is mixed with binder, it is complete using the microballoon that rotational forming machine rotational forming is the MFI topology that granularity is 20~400 μm
Silicalite molecular sieve catalyst；The rotary speed of rotational forming machine is 30-70rpm, and turntable inclination angle is 0-30 °.
D, the microballoon total silicon molecule sieve catalyst of MFI topology obtained in step c is roasted, after roasting
The microballoon total silicon molecule sieve catalyst of MFI topology contacted with the alkaline buffer solution of nitrogenous compound, then wash
It washs, filter, finished product after drying.
Preferably, mixing described in step a can carry out under conditions of temperature is 10-50 DEG C, the mixed time
It can be 0.5-10 hours.
Preferably, gained catalyst is on the basis of dry weight, including with 70~95wt% of dry basis containing micro-
Measure the silica zeolite of the MFI topology of rare earth ion and the binder of 5~30wt%；The partial size of the catalyst is
40~200 μm, abrasion index K is less than 5.
Preferably, the BET specific surface area of the silica zeolite of the MFI topology containing trace rare-earth ion is
400-500m2The weight ratio of silica and rare earth ion is (10000- in the silica zeolite of/g, MFI topology
200000)∶1。
Preferably, gained catalyst is on the basis of dry weight, including being opened up with the MFI of 80~90wt% of dry basis
Flutter the binder of the silica zeolite and 10~20wt% of learning structure.
Preferably, the binder can be silica solution, it can be acidic silicasol, be also possible to alkaline silica sol,
It is commercially available, can also be obtained according to any one prior art preparation, for example, by using being disclosed in patent CN1600428A
Method be prepared.Preferably, the binder is alkaline silica sol, the pH value of the alkaline silica sol is preferably 8.5~
13.5,9~12 are more highly preferred to, sodium ions content is preferably 10~500ppm, SiO2Content is preferably 25~45 weight %；Through
Gained SiO after roasting2Surface area be preferably 100-250m2/g。
Preferably, the rare earth ion is selected from Ce in step a3+、Ce4+、La3+At least one of；The rare earth from
Component is at least one of the nitrate containing the rare earth ion, chlorate, acetate and carbonate.
Preferably, the rare earth ion source is selected from La (NO3)3·6H2O、La(OAc)3·5H2O、LaCl3·7H2O、
La2(CO3)3·xH2O、Ce(NO3)3·6H2O、Ce(NO3)4·7H2O、Ce(OAc)3·5H2O、Ce(SO4)2·2H2O、
CeCl3·7H2At least one of O.
Preferably, the silicon source is selected from least one of silica gel, silica solution and organosilicon acid esters in step a；It is described
Organic formwork agent is selected from least one of fat amine compound, alcamine compound and quaternary amine alkaloid compound；Wherein, institute
The general formula for stating fat amine compound is R2(NH2)n, R2For the alkyl with 1-6 carbon atom, integer of the n between 1-3,
The general formula of the alcamine compound is (HOR3)mN, R3For the alkyl with 1-4 carbon atom, integer of the m between 1-3,
The alkyl quaternary amine alkali class compound has 1-4 carbon atom.
Preferably, the general formula of the organosilicon acid esters is (OR1)4Si, wherein R1For the alkyl of 1-4 carbon atom.
Methyl silicate and/or ethyl orthosilicate preferably, the organosilicon acid esters is positive；The organic formwork agent is alkane
Base quaternary amine alkaloid compound and/or fat amine compound；The alkyl quaternary amine alkali class compound is tetraethyl ammonium hydroxide
And/or tetrapropylammonium hydroxide；The fat amine compound is selected from ethamine, n-butylamine, n-propylamine, ethylenediamine and hexamethylene diamine
At least one of.
Preferably, the colloid admixture further includes low-carbon alcohols in step a, the low-carbon alcohols and SiO2Molar ratio
Be 1: (4-15), the low-carbon alcohols are ethyl alcohol.
Preferably, rotational forming is carried out in the case where addition has additive in step c, the additive is selected from field
Cyanines powder, graphite, active carbon, paraffin, stearic acid, glycerol, oxalic acid, tartaric acid, citric acid, starch, polyethylene glycol, polyethylene
Alcohol, polyethylene oxide, polypropylene amine, methyl cellulose, cellulose, polymeric alcohol, nitric acid, hydrochloric acid, acetic acid, formic acid, ammonium hydroxide, four
At least one of ammonium hydroxide, tetraethyl ammonium hydroxide and tetrapropylammonium hydroxide；The dosage of the additive is point
1~5wt% of son sieve dry weight.
Preferably, the alkaline buffer solution of the nitrogenous compound contains ammonium salt and alkali, the ammonium salt in step d
Content is 0.5-20wt%, and the content of the alkali is 5-30wt%, and the pH value of the alkaline buffer solution of the nitrogenous compound is
8.5-13.5。
Preferably, the ammonium salt is at least one of ammonium carbonate, ammonium fluoride, ammonium chloride, ammonium acetate and ammonium nitrate；Institute
Stating alkali is at least one of ammonium hydroxide, tetramethylammonium hydroxide, tetraethyl ammonium hydroxide and tetrapropylammonium hydroxide.
Preferably, the ammonium salt is ammonium acetate and/or ammonium nitrate；The alkali is ammonium hydroxide.
Preferably, the alkaline buffer of the molecular sieve and nitrogenous compound after the roasting in terms of butt is molten in step d
The weight ratio of liquid is 1: (5-15), the temperature of contact are 50-120 DEG C, and the pressure of contact is 0.5-5kg/cm2, the time of contact
It is 10-300 minutes, and determines whether that the alkaline buffer solution for being repeated several times nitrogenous compound post-processes depending on the performance of catalyst.
Preferably, in step d, the condition of the roasting are as follows: temperature is 200-600 DEG C, and the time is 1-20 hours.
A kind of preparation method of caprolactam, comprising: by cyclohexanone oxime in the presence of the solvent and made from preceding method
Catalyst contact carries out vapor phase beckmann rearrangement reaction.
Preferably, the molar ratio of the solvent and cyclohexanone oxime is (2-10): 1；The solvent is the rouge selected from C1-C6
Fat alcohol, preferably methanol and/or ethyl alcohol.
Preferably, the vapor phase beckmann rearrangement reaction carries out in the presence of nitrogen, the nitrogen and cyclohexanone oxime
Molar ratio be (10-80): 1.
Preferably, carrying out the condition of the vapor phase beckmann rearrangement reaction are as follows: the weight space velocity of cyclohexanone oxime is 0.1-
20 hours-1, reaction temperature is 300-500 DEG C, reaction pressure 0.1-0.5MPa.
With water in molar ratio it is 1 by cyclohexanone oxime preferably, this method further includes: after (0.01-2.5) is mixed,
It is contacted in the presence of the solvent with the catalyst again and carries out vapor phase beckmann rearrangement reaction.
By the microballoon total silicon molecule sieve catalyst disclosed by the invention containing the extremely MFI topology of trace rare-earth ion
When applied to Cyclohexanone-Oxime Gas Phase Beckmann Rearrangement, the selectivity of cyclohexanone oxime conversion ratio and caprolactam is higher, can be real
Existing caprolactam long period, continuous production, than existing total silicon molecule sieve catalyst have higher caprolactam overall selectivity and
Total recovery.And since by-product total amount declines, so that product separating energy consumption declines therewith, Technical Economy is effectively mentioned
It is high.
Embodiment 1
By 416kg ethyl orthosilicate, the tetrapropylammonium hydroxide of 360kg22.5 weight %, 14.6gCe (NO3)4·7H2O and
440kg water mixes, and stirs 5 hours under room temperature, forms the colloid admixture that pH value is 12.45, and mixture molar ratio is SiO2∶
TPAOH∶ H2O=1: 0.2: 20, SiO2With Ce3+Mass ratio be 30300: 1, said mixture is moved into 2m3Stainless steel reaction
In kettle, first hydrothermal crystallizing 1 day at 50 DEG C, then hydrothermal crystallizing 2 days at 100 DEG C, crystallization product pH value is 13.55, is then adopted
Film filtering is carried out with six periosteum of 50nm and is washed using 40~60 DEG C of water, and water consumption 7.0m is washed3, crystallization product
Washing water pH value reaches 9.1.The slurries concentration obtained after washing: 395kg solid content is the molecular sieve pulp of 26.8 weight %,
Microwave drying is sent to, it is 1 hour dry at 100~150 DEG C, obtain about 125kg silica zeolite original powder.
Above-mentioned -1 molecular sieve of total silicon roasts 6 hours at 550 DEG C, and the cerium ion content of sample is 32ppm, BET specific surface area
It is 442 meters2/ gram, Extra specific surface area is 58 meters2/ gram.
Above-mentioned silica zeolite original powder is crushed on pulverizer with 200 mesh screens, which repeats 2 times, obtains
The powder sample of 200~1000 mesh.The molecules of interest of 15kg200~1000 sieve powder sample is poured into the sugar coating machine of diameter 1.2m, sugar coating machine
10 ° of inclination angle, sugar coating machine revolving speed 50rpm inject the alkaline silica sol (pH value of 10.6kg30 weight % after rotating 5min several times
It is 9.5, sodium ions content 324ppm, SiO2Content is 40 weight %, gained SiO after being fired2Surface area be 225m2/g)
And spray it uniformly to powder, rotation stirring 60min, if obtain about 17kg granularity be 30~200 μm microballoon molecular sieve and
Dry kilogram other underproof materials, underproof material crushes on pulverizer again, as the raw material used next time.
By above-mentioned microballoon molecular sieve respectively in 280 DEG C, 400 DEG C, 480 DEG C of each roasting 2h, last 550 DEG C are roasted 12 hours, obtain about
10kg microballoon molecular sieve, wherein the content of the silica zeolite containing extremely trace rare-earth ion is 80 weight %, binder silicon
The content of colloidal sol is 20 weight %.
By the alkaline buffer solution (alkali of the nitrogenous compound of the above-mentioned microballoon molecular sieve of 100g and 1000g nitrogenous compound
Property buffer solution be ammonium hydroxide and aqueous ammonium nitrate solution mixed liquor, wherein the content of ammonium hydroxide is 26 weight %, and ammonium nitrate is water-soluble
The content of ammonium nitrate is 7.5 weight % in liquid, and the weight ratio of ammonium hydroxide and aqueous ammonium nitrate solution is 3: 2, pH value 11.35) it is added
To in 2L stainless steel cauldron (KCF-2 type magnetic agitation autoclave, Yantai high and new technology industrial development zone Ke Li automatic control equipment research institute), 82
℃、 2.3kg/cm2It stirs 1.5 hours under pressure, then filters, washing is 9 to cleaner liquid pH is crossed, then dry 24 at 120 DEG C
Hour, obtain microballoon molecular sieve catalyst, number A1.
The photo of catalyst A1 is shown in Fig. 1, it is seen that the catalyst forms the uniform microspheroidal of granule size；Its abrasion index
K=4.2；The test result of size distribution is shown in Table 1, it is seen then that the partial size of catalyst A1 concentrates on 40-200 μm.
Table 1
Embodiment 2
By 416kg ethyl orthosilicate, the tetrapropylammonium hydroxide of 360kg grams of 22.5 weight %, 28gCe (NO3)3·6H2O and
440kg water mixes, and stirs 5 hours under room temperature, forms the colloid admixture that pH value is 12.47, and mixture molar ratio is SiO2∶
TPAOH∶ H2O=1: 0.2: 20, SiO2With Ce 3+Mass ratio be 13500: 1, said mixture is moved into 2m3Stainless steel reaction
In kettle, first hydrothermal crystallizing 1.5 days at 50 DEG C, then hydrothermal crystallizing 1.5 days at 100 DEG C, crystallization product pH value is 13.73, so
Film filtering is carried out using six periosteum of 50nm afterwards and is washed using 40~60 DEG C of water, water consumption 6.7m is washed3, crystallization production
The washing water pH value of object reaches 9.1.The slurries concentration obtained after washing: the molecule that 310kg solid content is 34.5 weight % is obtained
Screening the pulp liquid, sends to microwave drying, 1 hour dry at 100~150 DEG C, obtains about 125kg silica zeolite original powder.
Above-mentioned -1 molecular sieve of total silicon roasts 6 hours at 550 DEG C, and the cerium ion content of sample is 73ppm, BET specific surface area
It is 434 meters2/ gram, Extra specific surface area is 56 meters2/ gram.
Above-mentioned silica zeolite original powder is crushed on pulverizer with 200 mesh screens, which repeats 2 times, obtains
The powder sample of 200~1000 mesh.The molecules of interest of 15kg200~1000 sieve powder sample is poured into the sugar coating machine of diameter 1.2m, sugar coating machine
15 ° of inclination angle, sugar coating machine revolving speed 60rpm inject the alkaline silica sol (pH value of 7.5kg30 weight % after rotating 5min several times
It is 9.5, sodium ions content 324ppm, SiO2Content is 40 weight %, gained SiO after being fired2Surface area be 225m2/g)
And spray it uniformly to powder, rotation stirring 60min, if obtain about 17kg granularity be 50~200 μm microballoon molecular sieve and
Dry kilogram other underproof materials, underproof material crushes on pulverizer again, as the raw material used next time.
By above-mentioned microballoon molecular sieve respectively in 280 DEG C, 400 DEG C, 480 DEG C of each roasting 2h, last 550 DEG C are roasted 12 hours, obtain about
10kg microballoon molecular sieve, wherein the content of the silica zeolite containing extremely trace rare-earth ion is 85 weight %, binder silicon
The content of colloidal sol is 15 weight %.
By the alkaline buffer solution (alkalinity of the nitrogenous compound of the above-mentioned microballoon molecular sieve of 95g and 950g nitrogenous compound
Buffer solution is the mixed liquor of ammonium hydroxide and ammonium acetate aqueous solution, wherein the content of ammonium hydroxide is 26 weight %, ammonium acetate aqueous solution
The content of middle ammonium acetate is 7.5 weight %, and the weight ratio of ammonium hydroxide and ammonium acetate aqueous solution is 3: 2, pH value 11.39) it is added to
In 2L stainless steel cauldron, in 90 DEG C, 2.8kg/cm2Stir 1.5 hours under pressure, then filter, 120 DEG C drying 24 hours,
The alkaline buffer solution touch operation for repeating above-mentioned nitrogenous compound under the same conditions later is primary, refilters, and washing is extremely
Crossing cleaner liquid pH is 9, then drying 24 hours at 120 DEG C, obtains microballoon molecular sieve catalyst, number A2.
The photo of catalyst A2 is similar with Fig. 1；Its abrasion index K=4.0；The test result of size distribution shows catalyst
The partial size of A2 concentrates on 40-200 μm.
Embodiment 3
By 416kg ethyl orthosilicate, the tetrapropylammonium hydroxide of 360kg22.5 weight %, 7.4 grams of Ce (OAc)3·5H2O and
440kg water mixes, and stirs 5 hours under room temperature, forms colloid admixture, forms the colloid admixture that pH value is 12.46, mixing
Object molar ratio is SiO2∶TPAOH∶H2O=1: 0.2: 20, SiO2With Ce 3+Mass ratio be 48000: 1, said mixture is moved
Enter 2m3In stainless steel cauldron, first hydrothermal crystallizing 1 day at 60 DEG C, then hydrothermal crystallizing 2 days at 100 DEG C, crystallization product pH
Value is 13.42, then carries out film filtering using six periosteum of 50nm and is washed using 40~60 DEG C of water, washs water consumption
6.7m3, the washing water pH value of crystallization product reaches 9.1.The slurries concentration obtained after washing: obtaining 310kg solid content is 28.4
The molecular sieve pulp of weight %, sends to microwave drying, 1 hour dry at 100~150 DEG C, obtains about 127kg silica zeolite
Original powder.
Above-mentioned -1 molecular sieve of total silicon roasts 6 hours at 550 DEG C, and the cerium ion content of sample is 21ppm, BET specific surface area
It is 442 meters2/ gram, Extra specific surface area is 62 meters2/ gram.
Above-mentioned silica zeolite original powder is crushed on pulverizer with 200 mesh screens, which repeats 2 times, obtains
The powder sample of 200~1000 mesh.The molecules of interest of 15kg200~1000 sieve powder sample is poured into the sugar coating machine of diameter 1.2m, sugar coating machine
20 ° of inclination angle, sugar coating machine revolving speed 50rpm inject the alkaline silica sol (pH value of 13.4kg30 weight % after rotating 5min several times
It is 9.5, sodium ions content 324ppm, SiO2Content is 40 weight %, gained SiO after being fired2Surface area be 225m2/g)
And spray it uniformly to powder, rotation stirring 60min, if obtain about 17kg granularity be 50~200 μm microballoon molecular sieve and
Dry kilogram other underproof materials, underproof material crushes on pulverizer again, as the raw material used next time.
By above-mentioned microballoon molecular sieve respectively in 280 DEG C, 400 DEG C, 480 DEG C of each roasting 2h, last 550 DEG C are roasted 12 hours, obtain about
10kg microballoon molecular sieve, wherein the content of the silica zeolite containing extremely trace rare-earth ion is 76 weight %, binder silicon
The content of colloidal sol is 24 weight %.
By the alkaline buffer solution (alkali of the nitrogenous compound of the above-mentioned microballoon molecular sieve of 100g and 1000g nitrogenous compound
Property buffer solution be ammonium hydroxide and aqueous ammonium nitrate solution mixed liquor, wherein the content of ammonium hydroxide is 26 weight %, and ammonium nitrate is water-soluble
The content of ammonium nitrate is 7.5 weight % in liquid, and the weight ratio of ammonium hydroxide and aqueous ammonium nitrate solution is 3: 2, pH value 11.35) it is added
Into 2L stainless steel cauldron, in 100 DEG C, 4.5kg/cm2It stirs 1.5 hours under pressure, then filters, 120 DEG C of dryings 24 are small
When, the alkaline buffer solution touch operation for repeating above-mentioned nitrogenous compound under the same conditions later is primary, refilters, and washs
It is 9 to cleaner liquid pH is crossed, then drying 24 hours at 120 DEG C, obtains microballoon molecular sieve catalyst, number A3.
The photo of catalyst A3 is similar with Fig. 1；Its abrasion index K=2.6；The test result of size distribution shows catalyst
The partial size of A3 concentrates on 40-200 μm.
Embodiment 4
By 416kg ethyl orthosilicate, the tetrapropylammonium hydroxide of 22.5 weight % of 720kg, 370kg ethyl alcohol, 40.4 grams of Ce
(NO3) 4·7H2O and 880kg water mixes, and stirs 5 hours under room temperature, forms the colloid admixture that pH value is 12.58, mixture
Molar ratio is SiO2∶TPAOH∶H2O=1: 0.4: 40, SiO2With Ce 4+Mass ratio be 10900: 1, ethyl alcohol/SiO2=8, it will
Said mixture moves into 5m3In stainless steel cauldron, first hydrothermal crystallizing 1 day at 50 DEG C, then the hydrothermal crystallizing 2 at 100 DEG C
It, crystallization product pH value is 13.80, then carries out film filtering using six periosteum of 50nm and is washed using 40~60 DEG C of water
It washs, washs water consumption 7.5m3, the washing water pH value of crystallization product reaches 9.1.The slurries concentration obtained after washing: 350kg is obtained
Solid content is the molecular sieve pulp of 30.7 weight %, sends to microwave drying, 1 hour dry at 100~150 DEG C, obtains about 127kg
Silica zeolite original powder.
Above-mentioned -1 molecular sieve of total silicon roasts 6 hours at 550 DEG C, and the cerium ion content of sample is 90ppm, BET specific surface area
It is 432 meters2/ gram, Extra specific surface area is 52 meters2/ gram.
Above-mentioned silica zeolite original powder is crushed on pulverizer with 200 mesh screens, which repeats 2 times, obtains
The powder sample of 200~1000 mesh.The molecules of interest of 15kg200~1000 sieve powder sample is poured into the sugar coating machine of diameter 1.2m, sugar coating machine
10 ° of inclination angle, sugar coating machine revolving speed 40rpm inject the alkaline silica sol (pH value of 10.5kg30 weight % after rotating 5min several times
It is 9.5, sodium ions content 324ppm, SiO2Content is 40 weight %, gained SiO after being fired2Surface area be 225m2/g)
And spray it uniformly to powder, rotation stirring 60min, obtain about 10kg granularity be 100~200 μm microballoon molecular sieve and
Several kilograms of other underproof materials, underproof material crushes on pulverizer again, as the former material used next time
Material.By above-mentioned microballoon molecular sieve respectively in 280 DEG C, 400 DEG C, 480 DEG C of each roasting 2h, last 550 DEG C are roasted 12 hours, obtain
About 10kg microballoon molecular sieve, wherein the content of the silica zeolite containing extremely trace rare-earth ion is 80 weight %, bonding
The content of agent silica solution is 20 weight %.
By the alkaline buffer solution (alkali of the nitrogenous compound of the above-mentioned microballoon molecular sieve of 100g and 1000g nitrogenous compound
Property buffer solution be ammonium hydroxide and aqueous ammonium nitrate solution mixed liquor, wherein the content of ammonium hydroxide is 26 weight %, and ammonium nitrate is water-soluble
The content of ammonium nitrate is 7.5 weight % in liquid, and the weight ratio of ammonium hydroxide and aqueous ammonium nitrate solution is 3: 2, pH value 11.35) it is added
Into 2L stainless steel cauldron, in 82 DEG C, 2.3kg/cm2It stirs 1.5 hours under pressure, then filters, 120 DEG C of dryings 24 are small
When, the alkaline buffer solution touch operation for repeating above-mentioned nitrogenous compound under the same conditions later is primary, refilters, washes
Washing to cleaner liquid pH is crossed is 9, then drying 24 hours at 120 DEG C, obtains microballoon molecular sieve catalyst, number A4.
The photo of catalyst A4 is similar with Fig. 1；Its abrasion index K=4.1；The test result of size distribution shows catalyst
The partial size of A4 concentrates on 40-200 μm.
Embodiment 5
By 208kg ethyl orthosilicate, the tetrapropylammonium hydroxide of 90kg22.5 weight %, 276kg ethyl alcohol, 24 grams of La (NO3)3·
6H2O and 110kg water mixes, and stirs 5 hours under room temperature, forms the colloid admixture that pH value is 12.91, and mixture molar ratio is
SiO2∶TPAOH∶H2O=1: 0.1: 10, SiO2With La3+Mass ratio be 15300: 1, ethyl alcohol/SiO2=10, by above-mentioned mixing
Object moves into 1m3In stainless steel cauldron, first hydrothermal crystallizing 2 days at 50 DEG C, then hydrothermal crystallizing 2 days at 100 DEG C, crystallization is produced
Object pH value is 13.48, then carries out film filtering using six periosteum of 50nm and is washed using 40~60 DEG C of water, washing water
Dosage 6.5m3, the washing water pH value of crystallization product reaches 9.1.The slurries concentration obtained after washing: obtaining 160kg solid content is
The molecular sieve pulp of 34.1 weight %, sends to microwave drying, 1 hour dry at 100~150 DEG C, obtains about 125kg total silicon point
Son sieve original powder.
Above-mentioned -1 molecular sieve of total silicon roasts 6 hours at 550 DEG C, and the lanthanum ion content of sample is 63ppm, BET specific surface area
It is 451 meters2/ gram, Extra specific surface area is 67 meters2/ gram.
Above-mentioned silica zeolite original powder is crushed on pulverizer with 200 mesh screens, which repeats 2 times, obtains
The powder sample of 200~1000 mesh.The molecules of interest of 15kg200~1000 sieve powder sample is poured into the sugar coating machine of diameter 1.2m, sugar coating machine
10 ° of inclination angle, sugar coating machine revolving speed 50rpm inject the alkaline silica sol (pH value of 4.8kg30 weight % after rotating 5min several times
It is 9.5, sodium ions content 324ppm, SiO2Content is 40 weight %, gained SiO after being fired2Surface area be 225m2/g)
And spray it uniformly to powder, rotation stirring 60min, if obtain about 8kg granularity be 100~200 μm microballoon molecular sieve and
Dry kilogram other underproof materials, underproof material crushes on pulverizer again, as the raw material used next time.
By above-mentioned microballoon molecular sieve respectively in 280 DEG C, 400 DEG C, 480 DEG C of each roasting 2h, last 550 DEG C are roasted 12 hours, obtain about
10.4kg microballoon molecular sieve, wherein the content of the silica zeolite containing extremely trace rare-earth ion is 90 weight %, binder
The content of silica solution is 10 weight %.
By the alkaline buffer solution (alkali of the nitrogenous compound of the above-mentioned microballoon molecular sieve of 100g and 1000g nitrogenous compound
Property buffer solution be ammonium hydroxide and aqueous ammonium nitrate solution mixed liquor, wherein the content of ammonium hydroxide is 26 weight %, and ammonium nitrate is water-soluble
The content of ammonium nitrate is 7.5 weight % in liquid, and the weight ratio of ammonium hydroxide and aqueous ammonium nitrate solution is 3: 2, pH value 11.4) it is added
Into 2L stainless steel cauldron, in 80 DEG C, 2.0kg/cm2It stirs 1.5 hours under pressure, then filters, washing to cleaner liquid excessively
PH is 9, then drying 24 hours at 120 DEG C, obtains microballoon molecular sieve catalyst, number A5.
The photo of catalyst A5 is similar with Fig. 1；Its abrasion index K=5.0；The test result of size distribution shows catalyst
The partial size of A5 concentrates on 40-200 μm.
Embodiment 6
By 416kg ethyl orthosilicate, the tetrapropylammonium hydroxide of 360kg22.5 weight %, 550kg ethyl alcohol, 2.6 grams of La
(OAc)3·5H2O and 260kg water mixes, and stirs 6 hours under room temperature, forms the colloid admixture that pH value is 12.85, mixture
Molar ratio is SiO2∶TPAOH∶H2O=1: 0.2: 15, SiO2With La3+Mass ratio be 140000: 1, ethyl alcohol/SiO2=10, it will
Said mixture moves into 3m3In stainless steel cauldron, first hydrothermal crystallizing 1 day at 60 DEG C, then the hydrothermal crystallizing 2 at 100 DEG C
It, crystallization product pH value is 13.55, then carries out film filtering using six periosteum of 50nm and is washed using 40~60 DEG C of water
It washs, washs water consumption 6.8m3, the washing water pH value of crystallization product reaches 9.1.The slurries concentration obtained after washing: it obtains
395kg solid content is the molecular sieve pulp of 26.8 weight %, sends to microwave drying, 1 hour dry at 100~150 DEG C, is obtained
About 120kg silica zeolite original powder.
Above-mentioned -1 molecular sieve of total silicon roasts 6 hours at 550 DEG C, and the lanthanum ion content of sample is 7ppm, BET specific surface area
It is 447 meters2/ gram, Extra specific surface area is 64 meters2/ gram.
Above-mentioned silica zeolite original powder is crushed on pulverizer with 200 mesh screens, which repeats 2 times, obtains
The powder sample of 200~1000 mesh.The molecules of interest of 15kg200~1000 sieve powder sample is poured into the sugar coating machine of diameter 1.2m, sugar coating machine
10 ° of inclination angle, sugar coating machine revolving speed 60rpm inject the alkaline silica sol (pH value of 10.6kg30 weight % after rotating 5min several times
It is 9.5, sodium ions content 324ppm, SiO2Content is 40 weight %, gained SiO after being fired2Surface area be 225m2/g)
And spray it uniformly to powder, rotation stirring 60min, obtain about 17kg granularity be 100~200 μm microballoon molecular sieve and
Several kilograms of other underproof materials.By above-mentioned microballoon molecular sieve respectively in 280 DEG C, 400 DEG C, 480 DEG C of each roasting 2h, most
It roasts 12 hours for 550 DEG C afterwards, obtains about 10kg microballoon molecular sieve, wherein the silica zeolite containing extremely trace rare-earth ion
Content be 80 weight %, the content of adhesive silicon sol is 20 weight %.
By the alkaline buffer solution (alkali of the nitrogenous compound of the above-mentioned microballoon molecular sieve of 100g and 1000g nitrogenous compound
Property buffer solution be ammonium hydroxide and aqueous ammonium nitrate solution mixed liquor, wherein the content of ammonium hydroxide is 26 weight %, and ammonium nitrate is water-soluble
The content of ammonium nitrate is 7.5 weight % in liquid, and the weight ratio of ammonium hydroxide and aqueous ammonium nitrate solution is 3: 2, pH value 11.35) it is added
Into 2L stainless steel cauldron, in 82 DEG C, 2.3kg/cm2It stirs 1.5 hours under pressure, then filters, 120 DEG C of dryings 24 are small
When, the alkaline buffer solution touch operation for repeating above-mentioned nitrogenous compound under the same conditions later is primary, refilters, washes
Washing to cleaner liquid pH is crossed is 9, then drying 24 hours at 120 DEG C, obtains microballoon molecular sieve catalyst, number A6.
The photo of catalyst A6 is similar with Fig. 1；Its abrasion index K=4.6；The test result of size distribution shows catalyst
The partial size of A6 concentrates on 40-200 μm.
It can be seen that the microballoon total silicon containing extremely trace rare-earth ion point disclosed by the invention from the result of embodiment 1-6
The abrasion index of sub- sieve catalyst is low, therefore can be used for the fluidisation that cyclohexanone oxime gas phase beckmann rearrangement prepares caprolactam
Bed process.
Testing example
This testing example is for illustrating that total silicon molecule sieve catalyst is in vapor phase beckmann rearrangement reaction prepared by embodiment 1-6
In catalysis reaction result.
Catalyst A1-A6 is respectively adopted and carries out Cyclohexanone-Oxime Gas Phase Beckmann Rearrangement in the following conditions:
Stainless steel fixed bed reactors carry out Cyclohexanone-Oxime Gas Phase Beckmann Rearrangement, the internal diameter 5mm of the reactor,
The catalyst of built-in 0.469 gram of 40~60 mesh loads the rubble sand of 30 mesh of about 30mm high, catalyst above catalyst bed
The fine quartz sand of 50 mesh is loaded below bed.Rearrangement reaction condition are as follows: normal pressure；380 DEG C of reaction temperature；Cyclohexanone oxime weight is empty
Speed (WHSV, catalyst weight in cyclohexanone oxime flow/bed in charging) is 16h-1；Reaction dissolvent is methanol, the methanol
Weight is the 65% of reaction raw materials weight；Carrier gas (N2) flow be 45ml/min, reaction product through mixture of ice and water cooling it is laggard
Enter receiving flask and carry out gas-liquid separation, carries out product composition analysis after reaction 6 hours.
Reaction product uses 6890 type gas chromatograph of Agilent company (hydrogen flame ion detector, PEG20M capillary color
Compose column, column length 50m) quantitative analysis is carried out, 250 DEG C of temperature of vaporization chamber, detection room temperature is 240 DEG C, and column temperature is temperature programming,
110 DEG C constant temperature 8 minutes, 15 DEG C/min is raised to 230 DEG C of constant temperature 14 minutes again.
The rearrangement product content of caprolactam and cyclonene is calculated using area normalization method after reaction, and solvent is not involved in product
Point.
Caprolactam in cyclohexanone oxime molar content and reaction product is obtained in reaction product by above-mentioned analysis
Molar content finds out cyclohexanone oxime conversion ratio and caprolactam selectivity according to following formula.The results are shown in Table 1.
Cyclohexanone oxime conversion ratio (mol%)=(cyclohexanone oxime molar content in 100- reaction product)/100 ×
100%
Caprolactam molar content/(100- reaction product middle ring in caprolactam overall selectivity (mol%)=reaction product
Hexanone oxime molar content) × 100%
In the by-product of Cyclohexanone-Oxime Gas Phase Beckmann Rearrangement, that own lactim accounts for about all by-products to methyl-ε-is total
40% or so of amount, the by-product is alcoholysis reaction occurs for the enol-type structure tautomer of methanol and caprolactam and gives birth to
At.Methyl-ε-own lactim continues to generate caprolactam through hydrolysis under the action of water.Therefore, it is calculating in oneself
It include the amount that methyl-ε-own lactim hydrolyzes and generates caprolactam when amide overall selectivity.
Table 2
| Catalyst number | Cyclohexanone oxime conversion ratio (mol%) | Caprolactam overall selectivity (mol%) |
| A1 | 99.45 | 95.25 |
| A2 | 99.22 | 95.61 |
| A3 | 98.72 | 96.75 |
| A4 | 99.01 | 96.26 |
| A5 | 99.38 | 95.80 |
| A6 | 98.63 | 96.31 |
From table 2 it can be seen that the present invention disclose it is obtained containing the extremely microballoon total silicon molecule sieve catalyst of trace rare-earth ion
Cyclohexanone oxime conversion ratio is higher, when cyclohexanone oxime weight space velocity (WHSV) is 16h-1When, highest can reach after reaction 6 hours
To 99.45%, and it is also very high to the selectivity of caprolactam, reach as high as 96.75%.
Raw materials used in the present invention, equipment is unless otherwise noted the common raw material, equipment of this field；In the present invention
Method therefor is unless otherwise noted the conventional method of this field.
The above is only presently preferred embodiments of the present invention, is not intended to limit the invention in any way, it is all according to the present invention
Technical spirit any simple modification, change and equivalent transformation to the above embodiments, still fall within the technology of the present invention side
The protection scope of case.
Claims (22)
1. a kind of rotational forming preparation side of the microballoon total silicon molecule sieve catalyst of the MFI topology containing trace rare-earth ion
Method, it is characterised in that the following steps are included:
A, silicon source, rare earth ion source, organic formwork agent and water are mixed, obtains colloid admixture；Wherein, the colloid admixture
Middle SiO2, organic formwork agent, water with molar ratio be 1:(0.05-0.50): (5-100)；In terms of silica, silicon source and rare earth
The mass ratio of ion is (10000-200000): 1；
B, the colloid admixture is first hydrothermal crystallizing 0.5-3 days at 50-60 DEG C, then the hydrothermal crystallizing 0.5- at 80-120 DEG C
3 days, gained crystallization product is carried out film filtering and washed to pH value to be 8-10, obtains the MFI containing trace rare-earth ion after dry
Topology silica zeolite；
C, the MFI topology by described containing trace rare-earth ion silica zeolite crush be 100 ~ 0000 mesh, then with
It is 20 ~ 400 (the microballoon total silicons of the MFI topology of m point that binder mixing, which is granularity using rotational forming machine rotational forming,
Sub- sieve catalyst；The rotary speed of rotational forming machine is 30-70rpm, and turntable inclination angle is 0-30 °；
D, the microballoon total silicon molecule sieve catalyst of MFI topology obtained in step c is roasted, after roasting
The microballoon total silicon molecule sieve catalyst of MFI topology is contacted with the alkaline buffer solution of nitrogenous compound, is washed out, mistake
Filter, finished product after drying.
2. rotational forming preparation method as described in claim 1, which is characterized in that gained catalyst is using dry weight as base
Standard, including with the silica zeolite of the MFI topology containing trace rare-earth ion of 70 ~ 95wt% of dry basis and 5 ~
The binder of 30wt%；The partial size of the catalyst is that 40 ~ 200 (m, abrasion index K is less than 5.
3. rotational forming preparation method as claimed in claim 2, which is characterized in that the MFI containing trace rare-earth ion is opened up
Flutterring and learning the BET specific surface area of the silica zeolite of structure is 400-500m2Two in the silica zeolite of/g, MFI topology
The weight ratio of silica and rare earth ion is (10000-200000): 1.
4. rotational forming preparation method as claimed in claim 2, which is characterized in that gained catalyst is using dry weight as base
Standard, including with the binder of the silica zeolite of the MFI topology of 80 ~ 90wt% of dry basis and 10 ~ 20wt%.
5. rotational forming preparation method as described in claim 1, which is characterized in that the binder is silica solution, the silicon
The sodium ions content of colloidal sol is 10-500ppm, SiO2Content is 20-45wt%.
6. rotational forming preparation method as described in claim 1, which is characterized in that in step a, the rare earth ion is selected from Ce3 +、Ce4+、La3+At least one of；The rare earth ion source is the nitrate containing the rare earth ion, chlorate, acetate
At least one of with carbonate.
7. rotational forming preparation method as claimed in claim 6, which is characterized in that the rare earth ion source is selected from La
(NO3)3·6H2O、La(OAc)3·5H2O、LaCl3·7H2O、La2(CO3)3·xH2O、Ce(NO3)3·6H2O、Ce(NO3)4·
7H2O、Ce(OAc)3·5H2O、Ce(SO4)2·2H2O、CeCl3·7H2At least one of O.
8. rotational forming preparation method as described in claim 1, which is characterized in that in step a, the silicon source be selected from silica gel,
At least one of silica solution and organosilicon acid esters；The organic formwork agent is selected from fat amine compound, alcamine compound
At least one of with quaternary amine alkaloid compound；Wherein, the general formula of the fat amine compound is R2(NH2)n, R2For with
The alkyl of 1-6 carbon atom, integer of the n between 1-3, the general formula of the alcamine compound are (HOR3)mN, R3For with 1-
The alkyl of 4 carbon atoms, integer of the m between 1-3, the alkyl quaternary amine alkali class compound have 1-4 carbon atom.
9. rotational forming preparation method as claimed in claim 8, which is characterized in that the general formula of the organosilicon acid esters is
(OR1)4Si, wherein R1For the alkyl of 1-4 carbon atom.
10. rotational forming preparation method as claimed in claim 9, which is characterized in that the organosilicon acid esters is positive silicic acid first
Ester and/or ethyl orthosilicate；The organic formwork agent is alkyl quaternary amine alkali class compound and/or fat amine compound；It is described
Alkyl quaternary amine alkali class compound is tetraethyl ammonium hydroxide and/or tetrapropylammonium hydroxide；The fat amine compound is selected from
At least one of ethamine, n-butylamine, n-propylamine, ethylenediamine and hexamethylene diamine.
11. rotational forming preparation method as described in claim 1, which is characterized in that in step a, the colloid admixture is also
Including low-carbon alcohols, the low-carbon alcohols and SiO2Molar ratio be 1:(4-15).
12. rotational forming preparation method as described in claim 1, which is characterized in that in step c, rotational forming has in addition
It is carried out in the case where additive, the additive is selected from sesbania powder, graphite, active carbon, paraffin, stearic acid, glycerol, oxalic acid, wine
Stone acid, citric acid, starch, polyethylene glycol, polyvinyl alcohol, polyethylene oxide, polypropylene amine, methyl cellulose, cellulose, polymerization
In alcohol, nitric acid, hydrochloric acid, acetic acid, formic acid, ammonium hydroxide, tetramethylammonium hydroxide, tetraethyl ammonium hydroxide and tetrapropylammonium hydroxide
It is at least one；The dosage of the additive is 1 ~ 5wt% of molecular sieve dry weight.
13. rotational forming preparation method as described in claim 1, which is characterized in that in step d, the nitrogenous compound
Alkaline buffer solution contains ammonium salt and alkali, and the content of the ammonium salt is 0.5-20wt%, and the content of the alkali is 5-30wt%, described
The pH value of the alkaline buffer solution of nitrogenous compound is 8.5-13.5.
14. rotational forming preparation method as claimed in claim 13, which is characterized in that the ammonium salt be ammonium carbonate, ammonium fluoride,
At least one of ammonium chloride, ammonium acetate and ammonium nitrate；The alkali is ammonium hydroxide, tetramethylammonium hydroxide, tetraethyl ammonium hydroxide
At least one of with tetrapropylammonium hydroxide.
15. rotational forming preparation method as claimed in claim 14, which is characterized in that the ammonium salt is ammonium acetate and/or nitre
Sour ammonium；The alkali is ammonium hydroxide.
16. rotational forming preparation method as described in claim 1, which is characterized in that the roasting in step d, in terms of butt
The weight ratio of the alkaline buffer solution of molecular sieve and nitrogenous compound after burning is 1:(5-15), the temperature of contact is 50-120
DEG C, the pressure of contact is 0.5-5kg/cm2, time of contact is 10-300 minute, and determines whether again depending on the performance of catalyst
The alkaline buffer solution post-processing of plural nitrogenous compound.
17. rotational forming preparation method as described in claim 1, which is characterized in that in step d, the condition of the roasting are as follows:
Temperature is 200-600 DEG C, and the time is 1-20 hours.
18. a kind of preparation method of caprolactam characterized by comprising by cyclohexanone oxime in the presence of the solvent with right
It is required that the contact of catalyst made from any one of 1-17 carries out vapor phase beckmann rearrangement reaction.
19. method as claimed in claim 18, which is characterized in that the molar ratio of the solvent and cyclohexanone oxime is (2-10):
1；The solvent is the fatty alcohol selected from C1-C6.
20. method as claimed in claim 18, which is characterized in that the vapor phase beckmann rearrangement reaction is in the presence of nitrogen
It carries out, the molar ratio of the nitrogen and cyclohexanone oxime is (10-80): 1.
21. method as claimed in claim 18, which is characterized in that carry out the condition of the vapor phase beckmann rearrangement reaction are as follows:
The weight space velocity of cyclohexanone oxime is 0.1-20 hours-1, reaction temperature is 300-500 DEG C, reaction pressure 0.1-0.5MPa.
22. method as claimed in claim 18, which is characterized in that this method further includes, in molar ratio by cyclohexanone oxime and water
After being mixed for 1:(0.01-2.5), then is contacted in the presence of the solvent with the catalyst and carry out gas phase Beckman weight
Row's reaction.
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