CN109718825A

CN109718825A - Microballoon Silicate-1 molecular sieve catalyst and preparation method thereof and the method for preparing caprolactam

Info

Publication number: CN109718825A
Application number: CN201711024212.3A
Authority: CN
Inventors: 程时标; 谢丽; 张树忠; 慕旭宏; 宗保宁
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2017-10-27
Filing date: 2017-10-27
Publication date: 2019-05-07
Anticipated expiration: 2037-10-27
Also published as: CN109718825B

Abstract

This disclosure relates to a kind of microballoon Silicate-1 molecular sieve catalyst containing trace metal ion and preparation method thereof and the method by preparing caprolactam with cyclohexanone-oxime, on the basis of the dry weight of catalyst, the catalyst includes the binder with the Silicate-1 molecular sieve containing trace metal ion of 70~95 weight % of dry basis and 5~30 weight %；The granularity of the catalyst is 20~300 μm, and abrasion index K is less than 8；The BET specific surface area of the Silicate-1 molecular sieve is 400-500 meters²/ gram, the weight ratio of silica and metal ion is (5000-200000): 1.The abrasion index of the catalyst is low, and the vapor phase beckmann rearrangement reaction for carrying out cyclohexanone oxime in fluidized-bed process can effectively improve the selectivity of caprolactam.

Description

Microballoon Silicate-1 molecular sieve catalyst and preparation method thereof and prepare caprolactam Method

Technical field

This disclosure relates to a kind of microballoon Silicate-1 molecular sieve catalyst and preparation method thereof containing trace metal ion With the method by preparing caprolactam with cyclohexanone-oxime.

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 a kind of with MFI Topology without -1 molecular sieve of aluminium total silicon, be to form a kind of simplest molecular sieve in ZSM-5 type structure molecular screen family, Its skeleton only contains silicon atom and oxygen atom, basic structural unit SiO₄Tetrahedron.- 1 molecular sieve of total silicon possesses abundant micro- Pore 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 material are applied to especially as molecular screen membrane Expect film, optical material film etc..Therefore, exploitation of -1 molecular sieve of total silicon in fields such as film adsorbing separation, purification, catalysis materials Using 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.American Association The research groups such as carbide company (UCC), Sweden Stety and India P.Ratnasamy once carried out research in this respect.They - 1 molecular sieve of total silicon is mainly used in inorganic microporous investigation of materials field.

Since -1 molecular sieve of total silicon is in extruded moulding, compression molding, or even roll molding etc. in the presence of very big difficulty, i.e., After making molding, the crushing strength of catalyst is very unsatisfactory (< 60N/cm or < 1kg/ particle), it is difficult to realize industrial applications.

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 It generallys use using the concentrated sulfuric acid or oleum as the liquid phase rearrangement technique of catalyst.The technique production caprolactam account for the world oneself 90% or so of lactams production, but the process requirement consumes a large amount of sulfuric acid and ammonium hydroxide, general every 1 ton of production is in oneself For amide 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 environment is dirty The problems such as dye.

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 the solid acid catalyst for being suitable for vapor phase beckmann rearrangement reaction, domestic and international researcher is 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 The silica-alumina catalyst used in GB881,927；The solid phosphoric acid catalysis used in British patent GB881,956 Agent；The catalyst of the boronic acid containing used in British patent GB1,178,057；The high silicon used in Chinese patent CN1269360A/ Aluminium is than MFI structure molecular sieve catalyst etc..Up to the present, fluidized-bed process is relatively suitble to vapor phase beckmann rearrangement reaction, micro- Ball 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 structure molecular sieve catalyst.The basic point of departure of this method is the specific side using acidic silica gel as binder Method is: by the water of siliceous oligomer made from alkoxyl silicone acidic hydrolysis and the subparticle of the MFI structure molecular sieve of pH≤5 or Alcohol-aqueous dispersions mixing makes emulsifying mixture, solidification, washing, roasts obtained gel micro-ball.The catalyst is suitable for 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 is Microspherical catalyst suitable for fluidized-bed reactor.

Since fluidized-bed process cost of investment is high, and cyclohexanone oxime only has 95% or so to be converted (to want in isolation technics Ask 100% conversion), therefore the fixed bed or moving bed new process of developing Cyclohexanone-Oxime Gas Phase Beckmann Rearrangement are as industry It is required using institute.Meanwhile the development applied to fixed bed or the preparation method of the spheric catalyst of moving bed process is also just mentioned In schedule.So far there is not yet by the Silicalite-1 molecular sieve containing trace metal ion rotated (rotation) at Type is microspheroidal and then related document, the patent for being applied to Cyclohexanone-Oxime Gas Phase Beckmann Rearrangement.

Summary of the invention

The Silicate-1 microballoon molecular sieve catalyst that purpose of this disclosure is to provide a kind of containing trace metal ion and its Preparation method and method by preparing caprolactam with cyclohexanone-oxime, the abrasion index of the catalyst is low, in fluidized-bed process The vapor phase beckmann rearrangement reaction for carrying out cyclohexanone oxime can effectively improve the selectivity of caprolactam.

To achieve the goals above, disclosure first aspect: a kind of microballoon Silicate- containing trace metal ion is provided 1 molecular sieve catalyst, on the basis of the dry weight of catalyst, which includes with 70~95 weight % of dry basis The binder of Silicate-1 molecular sieve containing trace metal ion and 5~30 weight %；The granularity of the catalyst is 20 ~300 μm, abrasion index K is less than 8；

The BET specific surface area of the Silicate-1 molecular sieve is 400-500 meters²/ gram, the weight of silica and metal ion Amount is than being (5000-200000): 1.

Optionally, on the basis of the dry weight of catalyst, which includes with 80~90 weight % of dry basis Silicate-1 molecular sieve and 10~20 weight % binder；

The granularity of the catalyst is 100~300 μm, and abrasion index K is less than 5.

Optionally, the metal ion is selected from Co²⁺、Ni²⁺、Cu²⁺、Zn²⁺、Fe²⁺、Mn²⁺、Cr³⁺、Fe³⁺、Ga³⁺、Al³⁺、 Ti⁴⁺、Zr⁴⁺、Sn⁴⁺、Ge⁴⁺、Pb⁴⁺、Mn⁴⁺、V⁵⁺、Sb⁵⁺、Mn⁶⁺、Mo⁶⁺And W⁶⁺At least one of；

The binder is silica solution, and the sodium ions content of the silica solution is 10-500ppm, SiO₂Content is 20-45 Weight %.

Disclosure second aspect: a kind of microballoon prepared described in disclosure first aspect containing trace metal ion is provided The method of Silicate-1 molecular sieve catalyst, this method comprises:

A, silicon source, metal ion source, organic formwork agent and water are mixed, obtains colloid admixture, wherein with molar ratio It counts, SiO in the colloid admixture₂: organic formwork agent: H₂O=1:(0.05-0.50): (5-100), silica and metal ion Weight ratio be (5000-200000): 1；

B, the colloid admixture obtained in step a is subjected to hydrothermal crystallizing 0.5- under 80-120 DEG C, self-generated pressure 10 days, it was 7.5-10 that gained crystallization product, which is washed to pH value, and the Silicate-1 containing trace metal ion points are obtained after dry Son sieve；

C, crushing the Silicate-1 molecular sieve containing trace metal ion obtained in step b is 60~500 mesh, Then it is mixed with binder, rotational forming is the microballoon molecular sieve that granularity is 20~300 μm；

The rotational forming carries out in the molding machine with eccentric agitating paddle, the staving of the molding machine can with it is described For agitating paddle at rotating backward, the molding machine has the bung to match with staving, is arranged on the bung towards staving inside There is the scraper towards bucket wall, for the material splashed on bucket wall to be struck off during the rotational forming, the molding machine Staving and vertical direction are in 20-40 ° of inclination angle；

D, microballoon molecular sieve obtained in step c is roasted, by the microballoon molecular sieve and nitrogenous compound after roasting Alkaline buffer solution contact, be washed out, filter, obtain microballoon molecular sieve catalyst after dry.

Optionally, in step a, the silicon source is selected from least one of silica gel, silica solution and organosilicon acid esters；It is preferred that It is (OR for general formula¹)₄The organosilicon acid esters of Si, wherein R¹For the alkyl of 1-4 carbon atom；More preferably methyl orthosilicate and/ Or ethyl orthosilicate；

The metal ion source is the nitrate containing the metal ion, chlorate, acetate, carbonate and esters Close at least one of object；

The organic formwork agent be in fat amine compound, alcamine compound and quaternary amine alkaloid compound extremely Few one kind；Preferably with the alkyl quaternary amine alkali class compound of 1-4 carbon atom；More preferably tetraethyl ammonium hydroxide and/or Tetrapropylammonium hydroxide.

Optionally, the colloid admixture in step a further includes low-carbon alcohols, the low-carbon alcohols and SiO₂Molar ratio be 1:(4-15), the low-carbon alcohols are methanol and/or ethyl alcohol.

Optionally, in step c, the revolving speed of the staving of the molding machine is 20-50rpm, and the revolving speed of the agitating paddle is 200-2000rpm。

Optionally, the condition of the roasting in step d are as follows: temperature is 200-600 DEG C, and the time is 1-20 hours.

Optionally, in step d, the alkaline buffer solution of the nitrogenous compound contains ammonium salt and alkali, and the ammonium salt contains Amount is 0.5-20 weight %, and the content of the alkali is 5-30 weight %, the pH value of the alkaline buffer solution of the nitrogenous compound For 8.5-13.5.

Optionally, in step d, the alkaline buffer of the microballoon molecular sieve and nitrogenous compound after the roasting in terms of butt The weight ratio of solution is 1:(5-15), the temperature of the contact is 50-120 DEG C, and the pressure of contact is 0.5-5kg/cm², contact Time be 10-300 minutes.

The disclosure third aspect: a kind of method by preparing caprolactam with cyclohexanone-oxime is provided, this method comprises: by hexamethylene Ketoxime in the presence of the solvent with the microballoon Silicate-1 molecular sieve described in disclosure first aspect containing trace metal ion Catalyst contact carries out vapor phase beckmann rearrangement reaction.

Optionally, the molar ratio of the solvent and cyclohexanone oxime is (2-10): 1；

The solvent is the fatty alcohol selected from C1-C6, preferably methanol and/or ethyl alcohol.

Optionally, the rearrangement reaction carries out in the presence of nitrogen, and the molar ratio of the nitrogen and cyclohexanone oxime is (10-80): 1.

Optionally, the condition of the rearrangement reaction is carried out 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.

Optionally, this method further includes, and with water is in molar ratio 1:(0.01-2.5 by cyclohexanone oxime) mixed after, then It is contacted in the presence of the solvent with the microballoon Silicate-1 molecular sieve catalyst containing trace metal ion and carries out gas Phase Beckmann rearrangement.

Through the above technical solutions, extremely micro metal is added in the disclosure in Silicate-1 sieve synthesis procedure Ion can effectively change the performance of Silicate-1 molecular sieve, then rotate (rotation) molding equipment by special strength Silicate-1 molecular sieve is formed, has obtained urging with the microballoon Silicate-1 molecular sieve of higher-strength and wearability Agent.In fluidized-bed reaction system, cyclohexanone oxime gas is carried out using the microballoon Silicate-1 molecular sieve catalyst of the disclosure Phase Beckmann rearrangement prepares caprolactam, is able to achieve caprolactam long period, continuous production, than existing Silicate-1 points Sub- sieve catalyst has higher caprolactam overall selectivity and total recovery, and since by-product total amount declines, product separation Energy consumption will also decline, and Technical Economy effectively improves.

Other feature and advantage of the disclosure will the following detailed description will be given in the detailed implementation section.

Detailed description of the invention

Attached drawing is and to constitute part of specification for providing further understanding of the disclosure, with following tool Body embodiment is used to explain the disclosure together, but does not constitute the limitation to the disclosure.In the accompanying drawings:

Fig. 1 is the photo of the microballoon molecular sieve Silicate-1 catalyst containing trace metal ion prepared by embodiment 1.

Specific embodiment

It is described in detail below in conjunction with specific embodiment of the attached drawing to the disclosure.It should be understood that this place is retouched The specific embodiment stated is only used for describing and explaining the disclosure, is not limited to the disclosure.

Disclosure first aspect: providing a kind of microballoon Silicate-1 molecular sieve catalyst containing trace metal ion, with On the basis of the dry weight of catalyst, which includes containing trace metal ion with 70~95 weight % of dry basis Silicate-1 molecular sieve and 5~30 weight % binder, it is preferable that on the basis of the dry weight of catalyst, this is urged Agent includes the binder with the Silicate-1 molecular sieve of 80~90 weight % of dry basis and 10~20 weight %.

The microballoon Silicate-1 molecular sieve catalyst that the disclosure provides has suitable granule size and higher wear-resistant Intensity.The granularity of the catalyst is 20~300 μm, preferably 100~300 μm.The abrasion index K of the catalyst less than 8, Further, the abrasion index K is less than 5, and the abrasion index K is lower, it was demonstrated that the abrasion resistance of catalyst is higher.

According to the disclosure, the BET specific surface area of the Silicate-1 molecular sieve can be 400-500 meters²/ gram, granularity Size can be 0.1-0.2 μm, and the weight ratio of silica and metal ion can be (5000-200000): 1.

According to the disclosure, the metal ion can be for selected from group ib, group iib, group ivb, Group VB, Section VI B Race, V Group IIB, group III A, group IVA and V A race metallic element ion.Preferably, the metal ion is choosing From Co²⁺、Ni²⁺、Cu²⁺、Zn²⁺、Fe²⁺、Mn²⁺、Cr³⁺、Fe³⁺、Ga³⁺、Al³⁺、Ti⁴⁺、Zr⁴⁺、Sn⁴⁺、Ge⁴⁺、Pb⁴⁺、Mn⁴⁺、V⁵⁺、Sb⁵ ⁺、Mn⁶⁺、Mo⁶⁺And W⁶⁺At least one of.

According to the disclosure, the binder can be silica solution, can be acidic silicasol, it is molten to be also possible to alkaline silicon Glue is commercially available, and can also be obtained according to any one prior art preparation, for example, by using public in patent CN1600428A The method opened is prepared.Preferably, the binder is alkaline silica sol, and 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。

According to the disclosure, the silicon source in step a can be the conventional selection of this field, such as can be for selected from silicon At least one of glue, silica solution and organosilicon acid esters；Preferably general formula is (OR¹)₄The organosilicon acid esters of Si, wherein R¹For 1- The alkyl of 4 carbon atoms；Further preferably methyl orthosilicate and/or ethyl orthosilicate.

According to the disclosure, the metal ion is the metal ion that is easy or can enter framework of molecular sieve, such as can be Selected from group ib, group iib, group ivb, Group VB, group VIB, V Group IIB, group III A, group IVA and V A race The ion of metallic element.Preferably, the metal ion is selected from Co²⁺、Ni²⁺、Cu²⁺、Zn²⁺、Fe²⁺、Mn²⁺、Cr³⁺、Fe³⁺、Ga³ ⁺、Al³⁺、Ti⁴⁺、Zr⁴⁺、Sn⁴⁺、Ge⁴⁺、Pb⁴⁺、Mn⁴⁺、V⁵⁺、Sb⁵⁺、Mn⁶⁺、Mo⁶⁺And W⁶⁺At least one of.It is highly preferred that institute The metal ion that is easy or can enter framework of molecular sieve that metal ion is trivalent or tetravalence is stated, such as can be for selected from Cr³⁺、 Fe³⁺、Ga³⁺、Al³⁺、Ti⁴⁺、Zr⁴⁺、Sn⁴⁺、Ge⁴⁺、Pb⁴⁺And Mn⁴⁺At least one of.It is further preferred that the metal ion For selected from Fe³⁺、Al³⁺、Ti⁴⁺And Zr⁴⁺At least one of.

According to the disclosure, the metal ion source in step a can be the compound containing above-mentioned metal ion, such as It can be the nitrate containing above-mentioned metal ion, chlorate, acetate, carbonate and ester type compound (such as tetraethyl titanate, titanium At least one of acid butyl ester etc.).It is special that the disclosure does not have the water soluble compound containing above-mentioned metal ion It is required that can be using any water soluble compound material containing above-mentioned metal ion being available commercially on the market, for example, working as Al is introduced to Silicate-1 molecular sieve³⁺When, it can be using materials such as SB powder, V250 powder, boehmite, C-1 powder.

According to the disclosure, the organic formwork agent in step a can be the conventional selection of this field, such as can be choosing From at least one of fat amine compound, alcamine compound and quaternary amine alkaloid compound.Wherein, the fatty amines The general formula for closing object is R²(NH₂)_n, R²For the alkyl with 1-6 carbon atom, integer of the n between 1-3, the fatty amines It closes object and is preferably selected from least one of ethamine, n-butylamine, n-propylamine, ethylenediamine and hexamethylene diamine.Wherein, the alcamines The general formula for closing object is (HOR³)_mN, R³For the alkyl with 1-4 carbon atom, integer of the m between 1-3, the alcamines chemical combination Object is preferably selected from least one of monoethanolamine, diethanol amine and triethanolamine.Wherein, the quaternary amine alkaloid compound is excellent It is selected as the alkyl quaternary amine alkali class compound with 1-4 carbon atom, further preferably tetraethyl ammonium hydroxide and/or tetrapropyl Ammonium hydroxide.

According to the disclosure, in step a, under preferable case, with molar ratio computing, SiO in the colloid admixture₂: You Jimo Plate agent: H₂O=1:(0.15-0.25): (10-50)；The mass ratio of silica and metal ion is (10000-100000): 1.

According to the disclosure, catalysis reaction is carried out in order to be more advantageous to molecular sieve, in the colloid admixture in step a It can also include low-carbon alcohols, the low-carbon alcohols and SiO₂Molar ratio can be 1:(4-15).Wherein, the low-carbon alcohols are methanol And/or ethyl alcohol.

According to the disclosure, mixing described in step a can carry out under conditions of temperature is 10-50 DEG C, when mixed Between can be 0.5-10 hours.

According to the disclosure, in step b, after the colloid admixture is carried out hydrothermal crystallizing, the pH value of crystallization product is about 13~14, then crystallization product can be carried out to film filtering be washed out, until pH value reaches the range of needs.Film filtering and The meaning of washing is well known to those skilled in the art, and the disclosure does not have special limitation.For example, can be using hot water to described Crystallization product carries out film filtering and washing, and the temperature of the hot water can be 20~70 DEG C, preferably 40~50 DEG C.The crystallization It is 8~9.5 that product, which is preferably washed to pH value,.The slurries of the resulting molecular sieve containing Silicate-1 can be concentrated into after washing point Son sieve content is dried again after being 10~40 weight %.

It is described containing micro in order to further obtain the microspherical catalyst of appropriate particle size size in step c according to the disclosure It is 100-250 mesh that the Silicate-1 molecular sieve of metal ion, which preferably crushes, is then mixed with binder.The mesh of binder is added Be in order to make molecular sieve powder particle rotation when be bonded to each other, to improve the intensity of shaping of catalyst product.It is viscous When tying agent additive amount deficiency, it is difficult to which balling-up will be crushed even if inadequate balling-up when leaving molding machine.When binder amount is excessive, Spherical product softens tacky.The binder can be the silica solution with certain solid content, such as can be solid content in 20- The alkaline silica sol of 50 weight %.Smashed molecular sieve powder can be mixed prior to binder, then put into molding machine in into Row rotational forming can also first put into smashed molecular sieve powder in molding machine, then described glue is added under stirring Tie agent.The dosage of the binder is to meet each component content of final catalyst obtained described in disclosure first aspect Condition subject to.

It is essential that the rotational forming in disclosed method, or be referred to as rotational forming, it is special at It is carried out in type machine.Smashed Silicate-1 molecular sieve powder and binder mix in the molding machine with eccentric agitating paddle It closes, the staving and agitating paddle of molding machine make molecular sieve powder and binder form aggregation stream under stiring at rotating backward.Institute The meaning for stating eccentric agitating paddle is well known to those skilled in the art, and off-centered position for example can be the stirring Paddle is the 1/3-3/4 of bucket radius at a distance from center.The bung to match with staving can ensure the leakproofness in bucket, lead to simultaneously Cross scraper to strike off the material splashed on bucket wall, reenter it in aggregation stream rotated in bucket, scraper and bucket wall away from It from more closely to ensure to realize above-mentioned purpose, such as can be 2~3mm.With counter-rotational continuous progress, material is in molding machine Middle formation molecular sieve seed, is then further formed spheric granules, until the granularity of spheric granules reaches required range Discharging obtains microballoon molecular sieve, that is to say, that the time rotated in molding machine by controlling material, can reach control molecule Sieve the purpose of microballoon size.The staving of molding machine and the inclination angle of vertical direction at an angle are more advantageous to needed for obtaining rapidly The microballoon molecular sieve of granularity, the inclination angle are more preferably 20~30 °.The staving diameter and height of molding machine can be according to realities Border needs to be designed.

According to the disclosure, in step c, by adjusting the revolving speed of molding machine and agitating paddle, be conducive to obtain required grain rapidly The microballoon molecular sieve of degree.For example, the revolving speed of the staving of the molding machine can be 20-50rpm, the revolving speed of the agitating paddle can be with For 200-2000rpm.There is no limit as long as meet the two to rotate backward for the agitating paddle and the respective rotation direction of molding machine ?.

According to the disclosure, the rotational forming in step c can be carried out in the case where addition has additive, described to add Add agent for example can be for selected from sesbania powder, graphite, active carbon, paraffin, stearic acid, glycerol, oxalic acid, tartaric acid, citric acid, shallow lake Powder, polyethylene glycol, polyvinyl alcohol, polyethylene oxide, polypropylene amine, methyl cellulose, cellulose, polymeric alcohol, nitric acid, hydrochloric acid, At least one of acetic acid, formic acid, ammonium hydroxide, tetramethylammonium hydroxide, tetraethyl ammonium hydroxide and tetrapropylammonium hydroxide are used Amount can be adjusted according to actual needs, and generally, the dosage of the additive is 1~5 weight of molecular sieve dry weight Measure %.Those skilled in the art should know, according to different needs, the additive can have it is modified or reaming Effect, or be conducive to form, but it can all volatilize in subsequent roasting process, will not remain on a catalyst, therefore In final catalyst obtained and additive component is not contained.

According to the disclosure, in step d, during the microballoon molecular sieve be roasted to preparing molecular sieve catalyst Conventional steps, condition can be with are as follows: temperature is 200-600 DEG C, and the time is 1-20 hours.

It,, can be in step d in order to make catalyst that there is higher intensity and higher catalytic activity according to the disclosure Microballoon molecular sieve after roasting is contacted with the alkaline buffer solution of nitrogenous compound.The alkaline buffer of the nitrogenous compound is molten Liquid can contain ammonium salt and alkali.The ammonium salt can be water soluble salt of ammonia, such as can be ammonium carbonate, ammonium fluoride, ammonium chloride, vinegar At least one of sour ammonium and ammonium nitrate, preferably ammonium acetate and/or ammonium nitrate are also possible to the quaternary amine of C1~C3 alkyl； The alkali can be at least one of ammonium hydroxide, tetramethylammonium hydroxide, tetraethyl ammonium hydroxide and tetrapropylammonium hydroxide, excellent It is selected as ammonium hydroxide.The ratio of the ammonium salt and alkali can be arbitrary, and can achieve the purpose of the disclosure, in order to enable the disclosure Microballoon Silicate-1 molecular sieve catalyst there is higher abrasion resistance and higher catalytic activity, the ammonium salt contains Amount is preferably 0.5-20 weight %, and the content of the alkali is preferably 5-30 weight %.The alkaline buffer of the nitrogenous compound is molten The pH value of liquid is preferably 8.5-13.5, more preferably 9-12.Microballoon molecular sieve after the roasting and nitrogen in terms of butt The weight ratio for closing the alkaline buffer solution of object can be 1:(5-15).The temperature of the contact can be 50-120 DEG C, contact Pressure can be 0.5-5kg/cm², the time of contact can be 10-300 minutes.The mode of the contact can the side of being arbitrary Formula preferably carries out in fixed bed reactors or reaction kettle.The alkali by microballoon molecular sieve and nitrogenous compound after roasting The operation of property buffer solution contact can carry out one or many.

It can after contacting the microballoon molecular sieve after roasting with the alkaline buffer solution of nitrogenous compound according to the disclosure The nitrogenous compound on microballoon molecular sieve catalyst surface is removed to be washed with the material of deionized water docking after touch, then Filtering, drying.As long as the drying sufficiently removes moisture, the method for the drying can be heat drying, air blast Dry, natural drying, the temperature of the drying can be 100~120 DEG C, and the dry time can be 10~24 hours.It will connect Material after touch wash and dry obtained catalyst is when for by preparing caprolactam with cyclohexanone-oxime, is conducive to mention High cyclohexanone oxime conversion ratio and caprolactam selectivity.

The disclosure third aspect provides a kind of method by preparing caprolactam with cyclohexanone-oxime, this method comprises: by hexamethylene The microballoon Silicate-1 molecular sieve containing trace metal ion that ketoxime is provided with first aspect present invention in the presence of the solvent Catalyst contact carries out vapor phase beckmann rearrangement reaction.

According to the disclosure, the molar ratio of the solvent and cyclohexanone oxime can be (2-10): 1.The solvent can be choosing From the fatty alcohol of 1-6 carbon atom, preferably methanol and/or ethyl alcohol.

According to the disclosure, the rearrangement reaction can carry out in the presence of nitrogen, and the nitrogen and cyclohexanone oxime rub Your ratio can be (10-80): 1, preferably (20-40): 1.In addition, being passed through a certain amount of NH in nitrogen₃、(CH₃)₃N etc. is nitrogenous Alkaline gas is beneficial to the rearrangement performance for improving catalyst.

According to the disclosure, the condition for carrying out the rearrangement reaction can be with are as follows: the weight space velocity (WHSV) of cyclohexanone oxime is 0.1-20 hours^-1, preferably 0.5-10 hours^-1；Reaction temperature be 300-500 DEG C, preferably 350-400 DEG C, more preferably 370-390℃；Reaction pressure is 0.1-0.5MPa.

According to the disclosure, a small amount of water is added in cyclohexanone oxime, the service life of catalyst can be extended, it therefore, can be by ring Hexanone oxime is 1:(0.01-2.5 with water in molar ratio) mixed after, then in the presence of the solvent with it is described contain trace meter The microballoon Silicate-1 molecular sieve catalyst contact of ion carries out vapor phase beckmann rearrangement reaction.

The microballoon Silicate-1 molecular sieve catalyst containing trace metal ion of the disclosure is applied to cyclohexanone oxime gas When phase Beckmann rearrangement, the selectivity of cyclohexanone oxime conversion ratio and caprolactam is higher, be able to achieve caprolactam long period, Continuous production has higher caprolactam overall selectivity and total recovery than existing Silicate-1 molecular sieve catalyst.And Since by-product total amount declines, so that product separating energy consumption declines therewith, Technical Economy effectively improves.

Below by embodiment, the present invention will be further described, but content not thereby limiting the invention.

The BET specific surface, Extra specific surface area data of Silicate-1 sieve sample are by the U.S. in embodiment Micromeritics ASAP-2400 type automatic absorbing instrument is made, test condition are as follows: N₂Make adsorbate, adsorption temp is- 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 AES measures the metal ion content of sample, test condition are as follows: with HF acid or aqua regia dissolution's solid Molecular sieve or catalyst make the silica volatility in sample, measure in aqueous solution.The size distribution of catalyst uses Dandong City The BT-9300S type laser fineness gage of hundred special Instrument Ltd. is measured, and test method is wet process test, and water work is situated between Matter, sample concentration: 0.5%~2%, scanning speed is 2000 times/second.The pattern of catalyst is taken pictures for regular handset.Catalyst Abrasion index K is according to the side RIPP29-90 in " petrochemical analysis method " (Yang Cuiding et al., Science Press, nineteen ninety) Method measures on wear index analyzer.

Embodiment 1

By 416kg ethyl orthosilicate, 22.5 weight % of 360kg tetrapropylammonium hydroxide (being abbreviated as TPAOH), 56.2gFe(NO₃)₃·9H₂O and 415kg water mixes, and stirs 5 hours under room temperature, forms the colloid admixture that pH value is 12.8, mixes Close SiO in object₂: TPAOH:H₂O (molar ratio)=1:0.2:20, SiO₂With Fe³⁺Weight ratio be 15347:1, by said mixture Move into 2m³In stainless steel cauldron, in 100 DEG C crystallization 3 days, crystallization product pH value be 13.57, then using six periosteum of 50nm into Row film filters and 40~60 DEG C of water is used to be washed, and washs water consumption 6.8m³The pH value of crystallization product reaches 9.1 afterwards.It is right The slurries concentration obtained after washing, obtains the molecular sieve pulp that 395kg solid content is 26.8 weight %, sends to microwave drying, 100~150 DEG C drying 1 hour, obtain about 125kg Silicate-1 molecular screen primary powder.

The iron ion content of above-mentioned Silicate-1 molecular sieve is 64ppm, and BET specific surface area is 446 meters²/ gram, it is outer to compare table Face is 61 meters²/ gram, granule size is 0.1~0.2 μm.

Above-mentioned Silicate-1 molecular screen primary powder is crushed on pulverizer with 80 mesh screens, obtains 100~250 mesh Powder sample.The molecules of interest of 15kg100~250 sieve powder sample is poured into (staving diameter 750mm, staving in 40L machinery strength forming machine With a vertical 30 ° of inclination angles) rotational forming is carried out, the staving of molding machine is rotated in the clockwise direction, revolving speed 30rpm, eccentric Agitating paddle rotates in the counterclockwise direction, mixing speed 1500rpm, injects 10.6kg30 weight % from feed inlet after rotation 5min Alkaline silica sol (pH value 9.5, sodium ions content 324ppm, SiO₂Content is 40 weight %, gained SiO after being fired₂ Surface area be 225m²/ g) and spray it uniformly to powder, Stirring 60min, obtaining about 17kg granularity is 100~300 μm microballoon molecular sieve and several kilograms of other underproof materials.By above-mentioned microballoon molecular sieve respectively 280 DEG C, 400 DEG C, 480 DEG C of each roasting 2h, last 550 DEG C roast 6 hours, obtain about 10kg microballoon molecular sieve, wherein contain trace metal ion The content of Silicate-1 molecular sieve is 80 weight %, and 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 be 26 weight %, aqueous ammonium nitrate solution The content of middle ammonium nitrate is 7.5 weight %, 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), 85 DEG C, 2.6kg/cm²Stir 3 hours under pressure, then filter, 120 DEG C drying 24 hours, repeat under the same conditions later above-mentioned The alkaline buffer solution touch operation of nitrogenous compound is primary, refilters, and washing is 9 to cleaner liquid pH is crossed, then is done at 120 DEG C Dry 24 hours, 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=4.4；The test result of size distribution is shown in Table 1, it is seen then that the partial size of catalyst A1 concentrates on 105-250 μm.

Table 1

Partial size (um)	Section %	Accumulate %	Partial size (um)	Section %	Accumulate %	Partial size (um)	Section %	Accumulate %	Partial size (um)	Section %	Accumulate %
												0.10-0.11	0	0	0.76-0.85	0	0	5.85-6.51	0	0	44.69-49.74	0	0
0.11-0.12	0	0	0.85-0.95	0	0	6.51-7.24	0	0	49.74-55.36	0	0
												0.12-0.14	0	0	0.95-1.05	0	0	7.24-8.06	0	0	55.36-61.62	0	0
0.14-0.15	0	0	1.05-1.17	0	0	8.06-8.97	0	0	61.62-68.58	0	0
												0.15-0.17	0	0	1.17-1.31	0	0	8.97-9.98	0	0	68.58-76.33	0	0
0.17-0.19	0	0	1.31-1.45	0	0	9.98-11.11	0	0	76.33-84.96	0	0
												0.19-0.21	0	0	1.45-1.62	0	0	11.11-12.37	0	0	84.96-94.56	0	0
0.21-0.24	0	0	1.62-1.80	0	0	12.37-13.77	0	0	94.56-105.24	0	0
												0.24-0.26	0	0	1.80-2.00	0	0	13.77-15.32	0	0	105.24-117.13	2.74	2.74
0.26-0.29	0	0	2.00-2.23	0	0	15.32-17.05	0	0	117.13-130.37	9.76	12.5
												0.29-0.32	0	0	2.23-2.48	0	0	17.05-18.98	0	0	130.37-145.10	16.41	28.91
0.32-0.36	0	0	2.48-2.76	0	0	18.98-21.12	0	0	145.10-161.50	19.71	48.62
												0.36-0.40	0	0	2.76-3.08	0	0	21.12-23.51	0	0	161.50-179.75	20.28	68.9
0.40-0.45	0	0	3.08-3.42	0	0	23.51-26.17	0	0	179.75-200.06	17.6	86.5
												0.45-0.50	0	0	3.42-3.81	0	0	26.17-29.12	0	0	200.06-222.66	10.57	97.07
0.50-0.55	0	0	3.81-4.24	0	0	29.12-32.41	0	0	222.66-247.83	2.93	100
												0.55-0.62	0	0	4.24-4.72	0	0	32.41-36.08	0	0	247.83-275.83	0	100
0.62-0.69	0	0	4.72-5.25	0	0	36.08-40.15	0	0	275.83-307.00	0	100
												0.69-0.76	0	0	5.25-5.85	0	0	40.15-44.69	0	0	307.00-341.69	0	100

Embodiment 2

By 416kg ethyl orthosilicate, 22.5 weight % of 360kg tetrapropylammonium hydroxide (being abbreviated as TPAOH), 0.236kgAl(NO₃)₃·9H₂O and 410kg water mixes, and stirs 5 hours under room temperature, forms the colloid that pH value is 12.35 and mixes Object, SiO in mixture₂: TPAOH:H₂O (molar ratio)=1:0.2:20, SiO₂With Al³⁺Weight ratio be 7067:1, will it is above-mentioned mix It closes object and moves into 2m³In stainless steel cauldron, in 100 DEG C crystallization 3 days, crystallization product pH value be 13.71, then using 50nm six manage Film is carried out film filtering and is washed using 40~60 DEG C of water, and water consumption 6.6m is washed³The pH value of crystallization product reaches afterwards 9.0.Slurries concentration to obtaining after washing, obtains the molecular sieve pulp that 310kg solid content is 34.5 weight %, it is dry to send to microwave It is dry, it is 1 hour dry at 100~150 DEG C, obtain about 125kg Silicate-1 molecular screen primary powder.

The aluminium composition of above-mentioned Silicate-1 molecular sieve is 140ppm, and BET specific surface area is 433 meters²/ gram, outer ratio Surface is 51 meters²/ gram, granule size is 0.1~0.2 μm.

Above-mentioned Silicate-1 molecular screen primary powder is crushed on pulverizer with 80 mesh screens, obtains 100~250 mesh Powder sample.The molecules of interest of 15kg100~250 sieve powder sample is poured into (staving diameter 750mm, staving in 40L machinery strength forming machine With a vertical 30 ° of inclination angles) rotational forming is carried out, the staving of molding machine is rotated in the clockwise direction, revolving speed 30rpm, eccentric Agitating paddle rotates in the counterclockwise direction, mixing speed 1500rpm, injects 7.5kg30 weight % from feed inlet after rotation 5min Alkaline silica sol (same as Example 1) and spray it uniformly to powder, Stirring 60min obtains about 17kg granularity For 100~300 μm of microballoon molecular sieves and several kilograms of other underproof materials.By above-mentioned microballoon molecular sieve respectively 280 DEG C, 400 DEG C, 480 DEG C of each roasting 2h, last 550 DEG C roast 6 hours, obtain about 10kg microballoon molecular sieve, wherein containing micro The content of the Silicate-1 molecular sieve of metal ion is 85 weight %, and the content of adhesive silicon 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 %, in ammonium acetate aqueous solution The content of 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 2L In stainless steel cauldron, in 90 DEG C, 3.0kg/cm²Stir 3 hours under pressure, then filter, 120 DEG C drying 24 hours, later The alkaline buffer solution touch operation for repeating above-mentioned nitrogenous compound under the same conditions is primary, refilters, washing to filtering Clear 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=4.4；The test result of size distribution shows catalyst The partial size of A2 concentrates on 100-300 μm.

Embodiment 3

By 416kg ethyl orthosilicate, 22.5 weight % of 360kg tetrapropylammonium hydroxide (being abbreviated as TPAOH), 8.4gZrOCl₂·8H₂O and 420kg water mixes, and stirs 5 hours under room temperature, forms the colloid admixture that pH value is 12.46, mixing SiO in object₂: TPAOH:H₂O (molar ratio)=1:0.2:20, SiO₂With Zr⁴⁺Weight ratio be 50596:1, said mixture is moved Enter 2m³In stainless steel cauldron, in 100 DEG C crystallization 3 days, crystallization product pH value be 13.42, then using six periosteum of 50nm carry out Film filters and 40~60 DEG C of water is used to be washed, and washs water consumption 6.7m³The pH value of crystallization product reaches 9.1 afterwards.To washing The slurries concentration obtained after washing, obtains the molecular sieve pulp that 310kg solid content is 28.4 weight %, microwave drying is sent to, 100 ~150 DEG C drying 1 hour, obtain about 127kg Silicate-1 molecular screen primary powder.

The zirconium ion content of above-mentioned Silicate-1 molecular sieve is 20ppm, and BET specific surface area is 428 meters²/ gram, it is outer to compare table Face is 48 meters²/ gram, granule size is 0.1~0.25 μm.

Above-mentioned Silicate-1 molecular screen primary powder is crushed on pulverizer with 80 mesh screens, obtains 100~250 mesh Powder sample.The molecules of interest of 15kg100~250 sieve powder sample is poured into (staving diameter 750mm, staving in 40L machinery strength forming machine With a vertical 30 ° of inclination angles) rotational forming is carried out, the staving of molding machine is rotated in the clockwise direction, revolving speed 30rpm, eccentric Agitating paddle rotates in the counterclockwise direction, mixing speed 1500rpm, injects 13.4kg30 weight % from feed inlet after rotation 5min Alkaline silica sol (same as Example 1) and spray it uniformly to powder, Stirring 60min obtains about 17kg granularity For 100~300 μm of microballoon molecular sieves and several kilograms of other underproof materials.By above-mentioned microballoon molecular sieve respectively 280 DEG C, 400 DEG C, 480 DEG C of each roasting 2h, last 550 DEG C roast 6 hours, obtain about 10kg microballoon molecular sieve, wherein containing micro The content of the Silicate-1 molecular sieve of metal ion is 76 weight %, and the content of adhesive silicon 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 be 26 weight %, aqueous ammonium nitrate solution The content of middle ammonium nitrate is 7.5 weight %, 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, in 100 DEG C, 4.0kg/cm²Stir 3 hours under pressure, then filter, 120 DEG C drying 24 hours, it The alkaline buffer solution touch operation for repeating above-mentioned nitrogenous compound under the same conditions afterwards is primary, refilters, washing to mistake Cleaner liquid pH is 9, 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=2.0；The test result of size distribution shows catalyst The partial size of A3 concentrates on 100-300 μm.

Embodiment 4

By 416kg ethyl orthosilicate, the tetrapropylammonium hydroxide (being abbreviated as TPAOH) of 22.5 weight % of 360kg, 50.4g Butyl titanate and 420kg water mix, and stir 5 hours under room temperature, form pH value for 12.32 colloid admixture, in mixture SiO₂: TPAOH:H₂O (molar ratio)=1:0.2:20, SiO₂With Ti⁴⁺Weight ratio be 16937:1, said mixture is moved into 2m³In stainless steel cauldron, in 100 DEG C crystallization 3 days, crystallization product pH value be 13.50, then using six periosteum of 50nm carry out film It filters and 40~60 DEG C of water is used to be washed, wash water consumption 6.8m³The pH value of crystallization product reaches 9 afterwards.After washing Obtained slurries concentration, obtains the molecular sieve pulp that 350kg solid content is 30.7 weight %, sends to microwave drying, 100~ 150 DEG C drying 1 hour, obtain about 127kg Silicate-1 molecular screen primary powder.

The titanium ion content of above-mentioned Silicate-1 molecular sieve is 60ppm, and BET specific surface area is 451 meters²/ gram, it is outer to compare table Face is 58 meters²/ gram, granule size is 0.1~0.25 μm.

Above-mentioned Silicate-1 molecular screen primary powder is crushed on pulverizer with 80 mesh screens, obtains 100~250 mesh Powder sample.The molecules of interest of 15kg100~250 sieve powder sample is poured into (staving diameter 750mm, staving in 40L machinery strength forming machine With a vertical 30 ° of inclination angles) rotational forming is carried out, the staving of molding machine is rotated in the clockwise direction, revolving speed 30rpm, eccentric Agitating paddle rotates in the counterclockwise direction, mixing speed 1500rpm, injects 10.5kg30 weight % from feed inlet after rotation 5min Alkaline silica sol (same as Example 1) and spray it uniformly to powder, Stirring 60min obtains about 10kg granularity For 100~300 μm of microballoon molecular sieves and several kilograms of other underproof materials.By above-mentioned microballoon molecular sieve respectively 280 DEG C, 400 DEG C, 480 DEG C of each roasting 2h, last 550 DEG C roast 6 hours, obtain about 10kg microballoon molecular sieve, wherein containing micro The content of the Silicate-1 molecular sieve of metal ion is 80 weight %, and 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 be 26 weight %, aqueous ammonium nitrate solution The content of middle ammonium nitrate is 7.5 weight %, 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, in 82 DEG C, 2.3kg/cm²Stir 3 hours under pressure, then filter, 120 DEG C drying 24 hours, it The alkaline buffer solution touch operation for repeating above-mentioned nitrogenous compound under the same conditions afterwards is primary, refilters, washing to mistake Cleaner liquid pH 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=3.1；The test result of size distribution shows catalyst The partial size of A4 concentrates on 100-300 μm.

Embodiment 5

By 208kg ethyl orthosilicate, the tetrapropylammonium hydroxide (being abbreviated as TPAOH) of 22.5 weight % of 360kg, 184kg Ethyl alcohol, 0.028gCr (NO₃)₃·9H₂O and 440kg water mixes, and stirs 5 hours under room temperature, and it is mixed to form the colloid that pH value is 12.94 Close object, SiO in mixture₂: TPAOH:H₂O (molar ratio)=1:0.4:40, ethyl alcohol: SiO₂(molar ratio)=8, SiO₂With Cr³⁺'s Weight ratio is 16483:1, and said mixture is moved into 2m³In stainless steel cauldron, in 100 DEG C crystallization 3 days, crystallization product pH value It is 13.50, film filtering is then carried out using six periosteum of 50nm and is washed using 40~60 DEG C of water, water consumption 7m is washed³ The pH value of crystallization product reaches 9 afterwards.Slurries concentration to obtaining after washing obtains point that 160kg solid content is 34.1 weight % Sub- screening the pulp liquid, sends to microwave drying, 1 hour dry at 100~150 DEG C, obtains about 125kg Silicate-1 molecular screen primary powder.

The content of chromium ion of above-mentioned Silicate-1 molecular sieve is 60ppm, and BET specific surface area is 433 meters²/ gram, it is outer to compare table Face is 52 meters²/ gram, granule size is 0.1~0.3 μm.

Above-mentioned Silicate-1 molecular screen primary powder is crushed on pulverizer with 80 mesh screens, obtains 100~250 mesh Powder sample.The molecules of interest of 15kg100~250 sieve powder sample is poured into (staving diameter 750mm, staving in 40L machinery strength forming machine With a vertical 30 ° of inclination angles) rotational forming is carried out, the staving of molding machine is rotated in the clockwise direction, revolving speed 30rpm, eccentric Agitating paddle rotates in the counterclockwise direction, mixing speed 1500rpm, injects 4.8kg30 weight % from feed inlet after rotation 5min Alkaline silica sol (same as Example 1) and spray it uniformly to powder, Stirring 60min, obtaining about 8kg granularity is 100~300 μm of microballoon molecular sieve and several kilograms of other underproof materials.By above-mentioned microballoon molecular sieve respectively 280 DEG C, 400 DEG C, 480 DEG C of each roasting 2h, last 550 DEG C roast 6 hours, obtain about 10.4kg microballoon molecular sieve, wherein contain micro gold The content for belonging to the Silicate-1 molecular sieve of ion is 90 weight %, and the content of adhesive silicon sol 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 be 26 weight %, aqueous ammonium nitrate solution The content of middle ammonium nitrate is 7.5 weight %, and the weight ratio of ammonium hydroxide and aqueous ammonium nitrate solution is 3:2, pH value 11.4) it is added to 2L In stainless steel cauldron, in 80 DEG C, 2.0kg/cm²Stir 3 hours under pressure, then filter, 120 DEG C drying 24 hours, later The alkaline buffer solution touch operation for repeating above-mentioned nitrogenous compound under the same conditions is primary, refilters, washing to filtering Clear liquid 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=7.5；The test result of size distribution shows catalyst The partial size of A5 concentrates on 100-300 μm.

Embodiment 6

By 416kg ethyl orthosilicate, 22.5 weight % of 360kg tetrapropylammonium hydroxide (being abbreviated as TPAOH), 56.2gFe(NO₃)₃·9H₂O and 415kg water mixes, and stirs 5 hours under room temperature, forms the colloid admixture that pH value is 12.8, mixes Close SiO in object₂: TPAOH:H₂O (molar ratio)=1:0.2:20, SiO₂With Fe³⁺Weight ratio be 15347:1, by said mixture Move into 2m³In stainless steel cauldron, in 100 DEG C crystallization 3 days, crystallization product pH value be 13.57, then using six periosteum of 50nm into Row film filters and 40~60 DEG C of water is used to be washed, and washs water consumption 6.8m³The pH value of crystallization product reaches 9.1 afterwards.It is right The slurries concentration obtained after washing, obtains the molecular sieve pulp that 395kg solid content is 26.8 weight %, sends to microwave drying, 100~150 DEG C drying 1 hour, obtain about 120kg Silicate-1 molecular screen primary powder.

The iron ion content of above-mentioned Silicate-1 molecular sieve is 64ppm, and BET specific surface area is 444 meters²/ gram, it is outer to compare table Face is 60 meters²/ gram, granule size is 0.1~0.2 μm.

Above-mentioned Silicate-1 molecular screen primary powder is crushed on pulverizer with 80 mesh screens, obtains 100~250 mesh Powder sample.The molecules of interest of 15kg100~250 sieve powder sample is poured into (staving diameter 750mm, staving in 40L machinery strength forming machine With a vertical 30 ° of inclination angles) rotational forming is carried out, the staving of molding machine is rotated in the clockwise direction, revolving speed 30rpm, eccentric Agitating paddle rotates in the counterclockwise direction, mixing speed 1500rpm, injects 10.6kg30 weight % from feed inlet after rotation 5min Alkaline silica sol (same as Example 1) and spray it uniformly to powder, Stirring 60min obtains about 17kg granularity For 100~300 μm of microballoon molecular sieves and several kilograms of other underproof materials.By above-mentioned microballoon molecular sieve respectively 280 DEG C, 400 DEG C, 480 DEG C of each roasting 2h, last 550 DEG C roast 6 hours, obtain about 10kg microballoon molecular sieve, wherein containing micro The content of the Silicate-1 molecular sieve of metal ion is 80 weight %, and 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 be 26 weight %, aqueous ammonium nitrate solution The content of middle ammonium nitrate is 7.5 weight %, 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, in 82 DEG C, 2.3kg/cm²Stir 3 hours under pressure, then filter, 120 DEG C drying 24 hours, it The alkaline buffer solution touch operation for repeating above-mentioned nitrogenous compound under the same conditions afterwards is primary, refilters, washing to mistake Cleaner liquid pH 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=5.0；The test result of size distribution shows catalyst The partial size of A6 concentrates on 100-300 μm.

It can be seen that the microballoon Silicate-1 molecule containing trace metal ion of the disclosure from the result of embodiment 1-6 The abrasion index of sieve catalyst is low, therefore can be used for the fluidized bed work that cyclohexanone oxime gas phase beckmann rearrangement prepares caprolactam Skill.

Testing example

This testing example is for illustrating that Silicate-1 molecular sieve catalyst is in gas phase Bake prepared by embodiment 1-6 Catalysis reaction result in graceful rearrangement reaction.

Catalyst A1-A6 is respectively adopted and carries out Cyclohexanone-Oxime Gas Phase Beckmann Rearrangement in the following conditions:

Cyclohexanone-Oxime Gas Phase Beckmann Rearrangement, the internal diameter of the reactor are carried out in stainless steel fixed bed reactors 5mm, the catalyst of built-in 0.469 gram of 40~60 mesh load the rubble sand of 30 mesh of about 30mm high, catalysis above catalyst bed The fine quartz sand of 50 mesh is loaded below agent 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 7 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 in caprolactam overall selectivity (mol%)=reaction product Middle cyclohexanone oxime molar content) × 100%

In the by-product of Cyclohexanone-Oxime Gas Phase Beckmann Rearrangement, methyl-ε-own lactim accounts for about all by-products 40% or so of object total amount, the by-product be the enol-type structure tautomer of methanol and caprolactam occur alcoholysis reaction and It generates.Methyl-ε-own lactim continues to generate caprolactam through hydrolysis under the action of water.Therefore, oneself is being calculated It include the amount that methyl-ε-own lactim hydrolyzes and generates caprolactam when lactams overall selectivity.

Table 1

As it can be seen from table 1 the microballoon Silicate-1 molecular sieve catalyst containing trace metal ion made from the disclosure Cyclohexanone oxime conversion ratio it is higher, when cyclohexanone oxime weight space velocity (WHSV) be 16h^-1When, highest can reach after reaction 7 hours To 99.25%, and it is also very high to the selectivity of caprolactam, reach as high as 96.76%.

The preferred embodiment of the disclosure is described in detail in conjunction with attached drawing above, still, the disclosure is not limited to above-mentioned reality The detail in mode is applied, in the range of the technology design of the disclosure, a variety of letters can be carried out to the technical solution of the disclosure Monotropic type, these simple variants belong to the protection scope of the disclosure.

It is further to note that specific technical features described in the above specific embodiments, in not lance In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the disclosure to it is various can No further explanation will be given for the combination of energy.

In addition, any combination can also be carried out between a variety of different embodiments of the disclosure, as long as it is without prejudice to originally Disclosed thought equally should be considered as disclosure disclosure of that.

Claims

1. a kind of microballoon Silicate-1 molecular sieve catalyst containing trace metal ion, which is characterized in that with the dry of catalyst On the basis of base weight amount, which includes with 70~95 weight % of dry basis containing trace metal ion The binder of Silicate-1 molecular sieve and 5~30 weight %；The granularity of the catalyst is 20~300 μm, abrasion index K Less than 8；

The BET specific surface area of the Silicate-1 molecular sieve is 400-500 meters²/ gram, the weight ratio of silica and metal ion For (5000-200000): 1.

2. catalyst according to claim 1, wherein on the basis of the dry weight of catalyst, the catalyst include with The Silicate-1 molecular sieve of 80~90 weight % of dry basis and the binder of 10~20 weight %；

3. catalyst according to claim 1 or 2, wherein the metal ion is selected from Co²⁺、Ni²⁺、Cu²⁺、Zn²⁺、 Fe²⁺、Mn²⁺、Cr³⁺、Fe³⁺、Ga³⁺、Al³⁺、Ti⁴⁺、Zr⁴⁺、Sn⁴⁺、Ge⁴⁺、Pb⁴⁺、Mn⁴⁺、V⁵⁺、Sb⁵⁺、Mn⁶⁺、Mo⁶⁺And W⁶⁺In It is at least one；

The binder is silica solution, and the sodium ions content of the silica solution is 10-500ppm, SiO₂Content is 20-45 weight Measure %.

4. a kind of microballoon Silicate-1 molecular sieve prepared described in any one of claim 1-3 containing trace metal ion The method of catalyst, which is characterized in that this method comprises:

A, silicon source, metal ion source, organic formwork agent and water are mixed, obtains colloid admixture, wherein with molar ratio computing, institute State SiO in colloid admixture₂: organic formwork agent: H₂O=1:(0.05-0.50): the weight of (5-100), silica and metal ion Amount is than being (5000-200000): 1；

B, the colloid admixture obtained in step a is carried out hydrothermal crystallizing 0.5-10 days under 80-120 DEG C, self-generated pressure, It is 7.5-10 that gained crystallization product, which is washed to pH value, obtains the Silicate-1 molecular sieve containing trace metal ion after dry；

The rotational forming carries out in the molding machine with eccentric agitating paddle, and the staving of the molding machine can be with the stirring For paddle at rotating backward, the molding machine has a bung to match with staving, is internally provided with court towards staving on the bung To the scraper of bucket wall, for striking off the material splashed on bucket wall during the rotational forming, the staving of the molding machine It is in 20-40 ° of inclination angle with vertical direction；

D, microballoon molecular sieve obtained in step c is roasted, by the alkali of microballoon molecular sieve and nitrogenous compound after roasting Property buffer solution contact, be washed out, filter, obtain microballoon molecular sieve catalyst after dry.

5. according to the method described in claim 4, wherein, in step a, the silicon source is selected from silica gel, silica solution and organosilicon At least one of acid esters；Preferably general formula is (OR¹)₄The organosilicon acid esters of Si, wherein R¹For the alkyl of 1-4 carbon atom； More preferably methyl orthosilicate and/or ethyl orthosilicate；

The metal ion source is the nitrate containing the metal ion, chlorate, acetate, carbonate and ester type compound At least one of；

The organic formwork agent is at least one in fat amine compound, alcamine compound and quaternary amine alkaloid compound Kind；Preferably with the alkyl quaternary amine alkali class compound of 1-4 carbon atom；More preferably tetraethyl ammonium hydroxide and/or 4 third Base ammonium hydroxide.

6. according to the method described in claim 4, wherein, the colloid admixture in step a further includes low-carbon alcohols, described low Carbon alcohol and SiO₂Molar ratio be 1:(4-15), the low-carbon alcohols be methanol and/or ethyl alcohol.

7. in step c, the revolving speed of the staving of the molding machine is 20-50rpm according to the method described in claim 4, wherein, The revolving speed of the agitating paddle is 200-2000rpm.

8. according to the method described in claim 4, wherein, the condition of the roasting in step d are as follows: temperature is 200-600 DEG C, Time is 1-20 hours.

9. according to the method described in claim 4, wherein, in step d, the alkaline buffer solution of the nitrogenous compound contains ammonium Salt and alkali, the content of the ammonium salt are 0.5-20 weight %, and the content of the alkali is 5-30 weight %, the nitrogenous compound The pH value of alkaline buffer solution is 8.5-13.5.

10. according to the method described in claim 4, wherein, the microballoon molecular sieve after the roasting in step d, in terms of butt Weight ratio with the alkaline buffer solution of nitrogenous compound is 1:(5-15), the temperature of the contact is 50-120 DEG C, contact Pressure is 0.5-5kg/cm², the time of contact is 10-300 minutes.

11. a kind of method by preparing caprolactam with cyclohexanone-oxime, this method comprises: by cyclohexanone oxime in the presence of the solvent with Microballoon Silicate-1 molecular sieve catalyst described in any one of claim 1-3 containing trace metal ion, which contacts, to carry out Vapor phase beckmann rearrangement reaction.

12. according to the method for claim 11, wherein the molar ratio of the solvent and cyclohexanone oxime is (2-10): 1；

13. according to the method for claim 11, wherein the rearrangement reaction carries out in the presence of nitrogen, the nitrogen Molar ratio with cyclohexanone oxime is (10-80): 1.

14. according to the method for claim 11, wherein carry out the condition of the rearrangement reaction are as follows: the weight of cyclohexanone oxime Air speed is 0.1-20 hours^-1, reaction temperature is 300-500 DEG C, reaction pressure 0.1-0.5MPa.

15. according to the method for claim 11, wherein this method further includes, and is in molar ratio 1 by cyclohexanone oxime and water: After (0.01-2.5) is mixed, then in the presence of the solvent with the microballoon Silicate-1 containing trace metal ion Molecular sieve catalyst contact carries out vapor phase beckmann rearrangement reaction.