CN102120589A - S-1 full-silicon molecular sieve and preparation method thereof as well as application of S-1 full-silicon molecular sieve in caprolactam preparation - Google Patents
S-1 full-silicon molecular sieve and preparation method thereof as well as application of S-1 full-silicon molecular sieve in caprolactam preparation Download PDFInfo
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Abstract
The invention discloses an S-1 full-silicon molecular sieve and a preparation method thereof as well as application of the S-1 full-silicon molecular sieve in caprolactam preparation. The S-1 full-silicon molecular sieve is prepared by the method comprising the following steps: (1) synthesizing a tetrapropylammonium hydroxide template agent; and (2) synthesizing a molecular sieve: carrying out a reaction on tetrapropylammonium hydroxide liquor and tetraethoxysilane and ethanol, filtering, washing with deionized water, drying reaction liquid, roasting, so as to obtain molecular sieve raw powder; adding silica sol, polyethylene glycol 2000, and stronger ammonia water, sesbania powder and activated carbon powder in the molecular sieve raw powder, kneading in a kneader, then carrying out extrusion; roasting, immersing the roasted product in a NH3-NH3NO3 mixing solution and a hydrofluoric acid solution respectively, washing with deionized water, drying, roasting again so as to obtain the S-1 full-silicon molecular sieve. In the invention, the template agent is cheap; the conversion rate of the cyclohexanone and selectivity of the caprolactam are extremely high; a catalyst can be easily and fast regenerated; and the use of concentrated sulphuric acid is avoided, thus the S-1 full-silicon molecular sieve and the preparation method thereof are environment-friendly.
Description
Technical field
The invention belongs to the petrochemical complex catalysis technical field, be specifically related to a kind of S-1 of utilization total silicon molecular sieve and carry out Beckman vapor phase rearrangement production hexanolactam pilot process.
Background technology
Hexanolactam is a kind of important chemical material, is the monomer of synthetic nylon 6 and engineering plastics.The operational path of synthesis of caprolactam mainly contains two kinds of liquid and gas Beckmann rearrangements at present.On industrial production, mainly be at present with sulfuric acid catalysis liquid phase rearrangement technology.This technology be cyclohexanone-oxime under the vitriol oil or oleum effect in certain temperature generation Beckmann rearrangement, utilize the acid hexanolactam that generates of ammonia neutralization reaction system then.This Technology comparatively maturation, reaction conditions mitigation, feed stock conversion and selectivity of product is all higher, but also has a lot of shortcomings.At first the vitriol oil is understood etching apparatus, understands discharge harmful in the production process, does not meet the idea of development of environmental protection; Simultaneously also can by-product a large amount of cheap ammonium sulfate (1 ton of hexanolactam of the every production of data presentation can by-product about 2 tons ammonium sulfate), economic benefit is relatively poor.Therefore, to increase economic efficiency and environmental benefit is the important directions that the novel hexanolactam synthesis technique of purpose becomes recent research.Though since the last century the eighties, people have reduced by changing reactor types and processing condition that vitriolic uses and the generation of ammonium sulfate, because the problem of sulfuric acid use generation is solved always at all.
In order to address the above problem, it is the gas phase beckmann rearrangement production technique of catalyzer that people begin one's study with the solid acid.This technology can avoid vitriolic to use fully, and the developing direction while production cost that therefore meets very much low-carbon environment-friendly also is expected to be reduced.Solid acid catalyst commonly used mainly contains oxide compound and molecular sieve two classes.Wherein USP5914398, USP3586668, USP5942613, USP4717769, USP4709024, Appl.Catal., 1999,188:361, J.Catal., 1994,148 (1): 138, Catal.Lett., 1998,49 (3-4): relevant reports such as 229 show that the oxide catalyst life-span is shorter, cyclohexanone-oxime transformation efficiency and hexanolactam selectivity are not high, and regeneration effect is bad, still do not have industrial value.For example, among the USP5914398 with amorphous little mesopore SiO
2-Al
2O
3Be catalyzer, at cyclohexanone-oxime weight space velocity (WHSV)=2.2h
-1Down, react after 23 hours, the cyclohexanone-oxime transformation efficiency reduces to 97.9%, and the hexanolactam selectivity only is 81.4%.People are the reaction effect of catalyzer in research with the molecular sieve also in addition.For example, J.Catal., 1992,137:252 is a catalyzer with S-1 total silicon molecular sieve, and the life-span, the cyclohexanone-oxime transformation efficiency was 90% less than 30h, and the hexanolactam selectivity is 81%; USP5403801 has reported the S-1 total silicon molecular sieve of handling through inorganic alkali solution, at WHSV=8h-1, reaction 6.25h cyclohexanone-oxime transformation efficiency is 99.5%, the hexanolactam selectivity is 96.5%, feeding the saturated air that contains methyl alcohol then regenerated 23 hours, after 30 times, the cyclohexanone-oxime transformation efficiency is 95.3% under the same reaction conditions repeatedly, and the hexanolactam selectivity is 95.3%.But perplexing the industrialized bottleneck of this technology at present is: hang down and the regeneration difficulty easily by inactivation, selectivity in the reaction of synthesis of caprolactam for (1) S-1 total silicon molecular sieve; (2) produce the needed template TPAOH of molecular sieve or quality is lower, or cost an arm and a leg (the general per kilogram of 20% aqueous solution is up to several thousand yuan), seriously restricted molecular sieve catalyst and prepared on a large scale.
To sum up, carrying out gas phase beckmann rearrangement production hexanolactam with S-1 total silicon molecular sieve catalyst has a good application prospect, but owing to there are some problems in the S-1 total silicon molecular sieve production process, cause the research of present this technology or can't reach better reaction effect, still rest on the laboratory lab scale stage, also have long road to walk apart from industrialization.
Summary of the invention
The purpose of this invention is to provide a kind of mass producible, meet the production method that S-1 total silicon molecular sieve prepares TPAOH template that require, cheap.
Second purpose of the present invention is to overcome deficiency of the prior art, and a kind of high conversion, highly selective, long lifetime of pilot scale, the preparation method of S-1 total silicon molecular sieve cheaply are provided.
The 3rd purpose of the present invention provides the application of S-1 total silicon molecular sieve in the preparation hexanolactam.
Technical scheme of the present invention is summarized as follows:
The preparation method of S-1 total silicon molecular sieve comprises the steps:
(1) the TPAOH template is synthetic:
201 * 7 resin anion(R.A) 100L are packed in the ion exchange column, be that 1-6m/h is that the hydrochloric acid of 2-6% and aqueous sodium hydroxide solution that the 10-100L massfraction is 2-6% carry out pre-treatment to described resin anion(R.A) with the 10-100L massfraction successively with the linear velocity, be 1-6m/h with the linear velocity again, be that the aqueous sodium hydroxide solution of 2-6% is regenerated to described resin anion(R.A) with the 100-800L massfraction; The regeneration back contains Na with the described resin anion(R.A) of deionized water wash to water outlet
+Content is below 100ppm; With the 100-300L massfraction is the 4-propyl bromide aqueous solution of 5-20%, is that 1-6m/h passes through ion exchange column with the linear velocity, and the TPAOH aqueous solution of collecting the acquisition of exchange back is standby;
(2) molecular sieve is synthetic:
With the 45-180L massfraction is that the TPAOH aqueous solution of 5%-20% is put into reactor, and rotating speed is under the stirring of 50-300 commentaries on classics/min; Tetraethoxy and alcoholic acid mixed solution in the speed adding reactor with 5-50L/h, are continued to stir 10-300min after adding is finished, close kettle cover; Speed with 1-15 ℃/min is warming up to 100-150 ℃, reacted 80-120 hour, reduce to room temperature, gained reaction solution membrane filtering method, with the pH=10-11 removal impurity of deionized water wash to filtrate, after the reaction solution drying behind the removal impurity,, obtain molecular screen primary powder at 500-650 ℃ of following roasting 4-8h; Described TPAOH, tetraethoxy and alcoholic acid mol ratio are 0.5-4: 2-16: 0.1-2;
In the molecular sieve of 40 mass parts, the massfraction that adds the 30-60 mass parts is the silicon sol of 10-25%, the Macrogol 2000 of 0.1-0.3 mass parts, the strong aqua of 10-40 mass parts, the field mountain valley with clumps of trees and bamboo powder of 1-3 mass parts and the active carbon powder of 1-2 mass parts, carries out extruded moulding after mediating with kneader; The gained bar takes out behind 500-650 ℃ of following roasting 4-8h;
Product after the roasting is put into the NH that mass ratio is 2-10: 2-10: 80-96 successively
3-NH
3NO
3-H
2The mixing solutions of O and massfraction be in the hydrofluoric acid aqueous solution of 0.01-0.08% in 80-95 ℃ of following immersion treatment 1-6h, with deionized water wash to the specific conductivity of elutant below 100 μ S/cm; Take out after drying and, take out encapsulation, promptly make a kind of S-1 total silicon molecular sieve once more in 500-650 ℃ of following roasting 4-8h.
S-1 total silicon molecular sieve is to make with method, and S-1 molecular sieve particle diameter is 100-200nm.
The application of S-1 total silicon molecular sieve in the preparation hexanolactam comprises the steps:
Get and put into reactor, filling with inert gas after 0.1-2g S-1 molecular sieve and 0.7-15g quartz sand mix; Being warming up to 400-550 ℃ of reaction 1-5h, being cooled to 330-390 ℃, under 0.1-0.3MP pressure, will pass through described beds in the presence of rare gas element by the mixing liquid that ammonia, water, cyclohexanone-oxime and methyl alcohol are formed with volume pump, is 1-8h at mass space velocity
-1Under carry out vapor phase beckmann rearrangement reaction and promptly get hexanolactam, keep reaction 200-600h and every the 1h sampling analysis; The mass ratio of ammonia, water, cyclohexanone-oxime and methyl alcohol is 0.006-0.06: 0.5-6: 30-90: 10-70 in the mixing liquid that described ammonia, water, cyclohexanone-oxime and methyl alcohol are formed.
Described rare gas element is argon gas, nitrogen or helium.
Reacted S-1 total silicon molecular sieve is regenerated, and described regenerated condition is: pressure 0.1-0.3MP, temperature 450-650 ℃, volume of air air speed 800-20000h
-1, recovery time 5-30h.
Advantage of the present invention is:
1) template is with low cost.Under the prerequisite that guarantees the molecular sieve quality, the template cost of being produced only is the 10%-30% of market value, and this has played very big pushing effect to the suitability for industrialized production of utilizing TPAOH to carry out molecular sieve as template.
2) cyclohexanone-oxime transformation efficiency and hexanolactam selectivity are all very high.With WHSV=2h
-1Be example, the transformation efficiency of cyclohexanone-oxime can be stablized and remains on more than 99.99% behind the reaction 400h, and the selectivity of hexanolactam is about 95.5%.
3) regeneration of catalyzer is very easy to and is quick, the active not obviously reduction of regeneration rear catalyst.The air that can feed certain flow rate to the catalyzer of inactivation reacts in-situ regeneration under 450-650 ℃, catalyzer need not be taken out, and has significantly reduced industrial labour intensity; Recovery time is short, just can realize regenerating according to the unusual 5-30h of air velocity; Behind the catalyst regeneration 3 times, at WHSV=2h
-1Behind the Shi Fanying 400h, the cyclohexanone-oxime transformation efficiency still is 99.99%, and the hexanolactam selectivity is about 95.5%.
4) owing to avoided the use of the vitriol oil, this preparing process of caprolactam is low for equipment requirements.
5) this produces the caprolactam technology environmental protection, meets the developing direction of energy-saving and emission-reduction.In the reaction by product seldom, solvent methanol can recycle after reclaiming.The cost of hexanolactam significantly reduces.
Description of drawings
The high power stereoscan photograph of Fig. 1 S-1 total silicon molecular sieve that to be method of the present invention produce according to embodiment 3.
Embodiment
The present invention is further illustrated below in conjunction with specific embodiment.
Embodiment 1:
A. the TPAOH template is synthetic:
201 * 7 resin anion(R.A) 100L are packed in the ion exchange column, be that 1m/h is that 6% hydrochloric acid and 10L massfraction are that 6% aqueous sodium hydroxide solution carries out pre-treatment to described resin anion(R.A) with the 10L massfraction successively with the linear velocity, be 2m/h with the linear velocity again, be that 6% aqueous sodium hydroxide solution is regenerated to resin anion(R.A) with the 100L massfraction; The regeneration back contains Na with the deionized water wash resin anion(R.A) to water outlet
+Content is below 100ppm; With the 100L massfraction is 5% the 4-propyl bromide aqueous solution, is that 1m/h passes through ion exchange column with the linear velocity, and it is standby to collect the TPAOH aqueous solution that the exchange back obtains.
Synthesizing of B.S-1 total silicon molecular sieve
The TPAOH aqueous solution 160L of massfraction 5% is put into reactor, open stirring rake, rotating speed is 50 commentaries on classics/min.Tetraethoxy and ethanol are added in the still with the speed of 20: 1 blended mixed solutions of mol ratio with 5L/h, continue stirring 10min finishing after, close kettle cover.Speed with 1 ℃/min is warming up to 100 ℃, stops behind the reaction 80h, reduces to room temperature, gained reaction solution membrane filtering method is with the pH=10-11 removal impurity of deionized water wash to filtrate, after the reaction solution drying behind the removal impurity, at 500 ℃ of following roasting 8h, obtain molecular screen primary powder; The mol ratio of described TPAOH and tetraethoxy is 1: 32;
It is 10% silicon sol, 100g Macrogol 2000,10kg strong aqua, 1kg field mountain valley with clumps of trees and bamboo powder and 1kg active carbon powder that the 40kg molecular sieve is added the 60kg massfraction, mediates the back extruded moulding with kneader, takes out behind 500 ℃ of following roasting 8h then.
It is 2: 2: 96 NH that product after the roasting is put into mass ratio successively
3-NH
3NO
3-H
2The mixing solutions of O and massfraction are to handle 6h down in 80 ℃ in 0.01% the hydrofluoric acid aqueous solution, with deionized water wash to the specific conductivity of elutant below 100 μ S/cm; Take out after drying and, take out encapsulation, promptly make a kind of S-1 total silicon molecular sieve once more in 500 ℃ of following roasting 8h.S-1 molecular sieve particle diameter is 100-200nm.
C. hexanolactam is synthetic
Get and put into reactor after S-1 molecular sieve 0.1g and 0.7g quartz sand mix, the usefulness argon gas to catalyst pretreatment 5h, is cooled to 330 ℃ then and reacts under 0.1MP pressure under 400 ℃, and WHSV is controlled at 1h
-1To pass through described beds in the presence of rare gas element by the mixing liquid that ammonia, water, cyclohexanone-oxime and methyl alcohol are formed with volume pump, the mass ratio of ammonia, water, cyclohexanone-oxime and methyl alcohol is 0.006: 0.5: 30 in the mixing liquid that described ammonia, water, cyclohexanone-oxime and methyl alcohol are formed: 70.Behind catalyst deactivation, feed volume space velocity 20000h
-1Air under 0.1MP, 650 ℃ to the catalyzer 5h that regenerates.
Reaction result is that behind the reaction 400h, still more than 99.98%, selectivity is about 95.1% for transformation efficiency.After reaction 400h was continued in the regeneration back, its transformation efficiency was 99.96%, and selectivity is 95.1%.
Embodiment 2:
A. template is synthetic
201 * 7 resin anion(R.A) 100L are packed in the ion exchange column, be that 2m/h is that 4% hydrochloric acid and 100L massfraction are that 4% aqueous sodium hydroxide solution carries out pre-treatment to described resin anion(R.A) with the 100L massfraction successively with the linear velocity, be 1m/h with the linear velocity again, be that 6% aqueous sodium hydroxide solution is regenerated to resin anion(R.A) with the 600L massfraction; The regeneration back contains Na with the deionized water wash resin anion(R.A) to water outlet
+Content is below 100ppm; With the 100L massfraction is 8% the 4-propyl bromide aqueous solution, is that 2m/h passes through ion exchange column with the linear velocity, and it is standby to collect the TPAOH aqueous solution that the exchange back obtains.
Synthesizing of B.S-1 total silicon molecular sieve
The TPAOH aqueous solution 100L of massfraction 10% is put into reactor, open stirring rake, rotating speed is 100 commentaries on classics/min.Tetraethoxy and ethanol are added in the still with the speed of 10: 1 blended mixed solutions of mol ratio with 20L/h, continue stirring 90min finishing after, close kettle cover.Speed with 4 ℃/min is warming up to 110 ℃, reacts to stop after 100 hours.Reduce to room temperature, gained reaction solution membrane filtering method with the pH=10-11 removal impurity of deionized water wash to filtrate, after the reaction solution drying behind the removal impurity, at 550 ℃ of following roasting 6h, obtains molecular screen primary powder; The mol ratio of described TPAOH and tetraethoxy is 1: 8;
It is 15% silicon sol, 200g Macrogol 2000,20kg strong aqua, 2kg field mountain valley with clumps of trees and bamboo powder and 1.5kg active carbon powder that the 40kg molecular sieve is added the 40kg massfraction, mediates the back extruded moulding with kneader, takes out behind 600 ℃ of following roasting 6h then.
It is 5: 5: 90 NH that product after the roasting is put into mass ratio successively
3-NH
3NO
3-H
2The mixing solutions of O and massfraction are to handle 5h down in 85 ℃ in 0.02% the hydrofluoric acid aqueous solution, with deionized water wash to the specific conductivity of elutant below 100 μ S/cm; Take out after drying and, take out encapsulation, promptly make a kind of S-1 total silicon molecular sieve once more in 550 ℃ of following roasting 6h.S-1 molecular sieve particle diameter is 100-200nm.
C. hexanolactam is synthetic
Get and put into reactor after S-1 molecular sieve 0.5g and 3g quartz sand mix, usefulness nitrogen to catalyst pretreatment 3h, is cooled to 350 ℃ then and reacts under 0.2MP pressure under 450 ℃, and WHSV is controlled at 2h
-1To pass through described beds in the presence of rare gas element by the mixing liquid that ammonia, water, cyclohexanone-oxime and methyl alcohol are formed with volume pump, the mass ratio of ammonia, water, cyclohexanone-oxime and methyl alcohol is 0.02: 2: 40 in the mixing liquid that described ammonia, water, cyclohexanone-oxime and methyl alcohol are formed: 60.Behind catalyst deactivation, feed volume space velocity 5000h
-1Air under 0.2MP, 600 ℃ to the catalyzer 20h that regenerates.
Reaction result is that behind the reaction 400h, still more than 99.99%, selectivity is about 95.5% for transformation efficiency.After reaction 400h was continued in the regeneration back, its transformation efficiency still was 99.99%, and selectivity is 95.3%.
Embodiment 3:
A. template is synthetic
201 * 7 resin anion(R.A) 100L are packed in the ion exchange column, be that 3m/h is that 4% hydrochloric acid and 100L massfraction are that 4% aqueous sodium hydroxide solution carries out pre-treatment to described resin anion(R.A) with the 100L massfraction successively with the linear velocity, be 3m/h with the linear velocity again, be that 5% aqueous sodium hydroxide solution is regenerated to resin anion(R.A) with the 500L massfraction; The regeneration back contains Na with the deionized water wash resin anion(R.A) to water outlet
+Content is below 100ppm; With the 250L massfraction is 15% the 4-propyl bromide aqueous solution, is that 3m/h passes through ion exchange column with the linear velocity, and it is standby to collect the TPAOH aqueous solution that the exchange back obtains.
Synthesizing of B.S-1 total silicon molecular sieve
The TPAOH aqueous solution 180L of massfraction 5% is put into reactor, open stirring rake, rotating speed is 200 commentaries on classics/min.Tetraethoxy and ethanol are added in the still with the speed of 18: 1 blended mixed solutions of mol ratio with 30L/h, continue stirring 200min finishing after, close kettle cover.Speed with 10 ℃/min is warming up to 130 ℃, reacts to stop after 100 hours, reduces to room temperature, gained reaction solution membrane filtering method is with the pH=10-11 removal impurity of deionized water wash to filtrate, after the reaction solution drying behind the removal impurity, at 600 ℃ of following roasting 5h, obtain molecular screen primary powder; The mol ratio of described TPAOH and tetraethoxy is 3: 16;
It is 20% silicon sol, 250g Macrogol 2000,30kg strong aqua, 2.5kg field mountain valley with clumps of trees and bamboo powder and 1.6kg active carbon powder that the 40kg molecular sieve is added the 50kg massfraction, mediates the back extruded moulding with kneader, takes out behind 600 ℃ of following roasting 6h then.
It is 8: 8: 84 NH that product after the roasting is put into mass ratio successively
3-NH
3NO
3-H
2The mixing solutions of O and massfraction are to handle 2h down in 90 ℃ in 0.06% the hydrofluoric acid aqueous solution, with deionized water wash to the specific conductivity of elutant below 100 μ S/cm; Take out after drying and, take out encapsulation, promptly make a kind of S-1 total silicon molecular sieve once more in 600 ℃ of following roasting 5h.S-1 molecular sieve particle diameter is 100-200nm.
C. hexanolactam is synthetic
Get and put into reactor after S-1 molecular sieve 1g and 8g quartz sand mix, the usefulness helium to catalyst pretreatment 4h, is cooled to 360 ℃ then and reacts under 0.3MP pressure under 500 ℃, and WHSV is controlled at 4h
-1To pass through described beds in the presence of rare gas element by the mixing liquid that ammonia, water, cyclohexanone-oxime and methyl alcohol are formed with volume pump, the mass ratio of ammonia, water, cyclohexanone-oxime and methyl alcohol is 0.04: 4: 60 in the mixing liquid that described ammonia, water, cyclohexanone-oxime and methyl alcohol are formed: 40.Behind catalyst deactivation, feed volume space velocity 15000h
-1Air under 0.25MP, 600 ℃ to the catalyzer 10h that regenerates.
Reaction result is that behind the reaction 400h, still more than 99.97%, selectivity is about 95.6% for transformation efficiency.After reaction 400h was continued in the regeneration back, its transformation efficiency still was 99.94%, and selectivity is 95.4%.
Embodiment 4:
A. template is synthetic
201 * 7 resin anion(R.A) 100L are packed in the ion exchange column, be that 6m/h is that 2% hydrochloric acid and 100L massfraction are that 2% aqueous sodium hydroxide solution carries out pre-treatment to described resin anion(R.A) with the 100L massfraction successively with the linear velocity, be 6m/h with the linear velocity again, be that 2% aqueous sodium hydroxide solution is regenerated to resin anion(R.A) with the 800L massfraction; The regeneration back contains Na with the deionized water wash resin anion(R.A) to water outlet
+Content is below 100ppm; With the 300L massfraction is 20% the 4-propyl bromide aqueous solution, is that 6m/h passes through ion exchange column with the linear velocity, and it is standby to collect the TPAOH aqueous solution that the exchange back obtains.
Synthesizing of B.S-1 total silicon molecular sieve
The TPAOH aqueous solution 45L of massfraction 20% is put into reactor, open stirring rake, rotating speed is 300 commentaries on classics/min.Tetraethoxy and ethanol are added in the still with the speed of 8: 1 blended mixed solutions of mol ratio with 50L/h, continue stirring 300min finishing after, close kettle cover.Speed with 15 ℃/min is warming up to 150 ℃, reacts to stop after 120 hours.Reduce to room temperature.Gained reaction solution membrane filtering method with the pH=10-11 removal impurity of deionized water wash to filtrate, after the reaction solution drying behind the removal impurity, at 650 ℃ of following roasting 4h, obtains molecular screen primary powder; Described TPAOH and tetraethoxy and alcoholic acid mol ratio are 1: 4;
It is 25% silicon sol, 300g Macrogol 2000,40kg strong aqua, 3kg field mountain valley with clumps of trees and bamboo powder and 2kg active carbon powder that the 40kg molecular sieve is added the 30kg massfraction, mediates the back extruded moulding with kneader, takes out behind 650 ℃ of following roasting 4h then.
It is 10: 10: 80 NH that product after the roasting is put into mass ratio successively
3-NH
3NO
3-H
2The mixing solutions of O and massfraction are to handle 1h down in 95 ℃ in 0.08% the hydrofluoric acid aqueous solution, with deionized water wash to the specific conductivity of elutant below 100 μ S/cm; Take out after drying and, take out encapsulation, promptly make a kind of S-1 total silicon molecular sieve once more in 650 ℃ of following roasting 4h.S-1 molecular sieve particle diameter is 100-200nm.
C. hexanolactam is synthetic
Get and put into reactor after S-1 molecular sieve 2g and 15g quartz sand mix, usefulness nitrogen to catalyst pretreatment 1h, is cooled to 390 ℃ then and reacts under 0.1MP pressure under 550 ℃, and WHSV is controlled at 8h
-1To pass through described beds in the presence of rare gas element by the mixing liquid that ammonia, water, cyclohexanone-oxime and methyl alcohol are formed with volume pump, the mass ratio of ammonia, water, cyclohexanone-oxime and methyl alcohol is 0.06: 6: 90 in the mixing liquid that described ammonia, water, cyclohexanone-oxime and methyl alcohol are formed: 10.Behind catalyst deactivation, feed volume space velocity 800h
-1Air under 0.3MP, 450 ℃ to the catalyzer 30h that regenerates.
Reaction result is that behind the reaction 400h, still more than 99.92%, selectivity is about 95.1% for transformation efficiency.After reaction 400h was continued in the regeneration back, its transformation efficiency still was 99.89%, and selectivity is 95.1%.
The high power stereoscan photograph of the S-1 total silicon molecular sieve of embodiment 1, embodiment 2 or embodiment 4 preparations is similar to Fig. 1.
Claims (5)
1.S-1 the preparation method of total silicon molecular sieve is characterized in that comprising the steps:
(1) the TPAOH template is synthetic:
201 * 7 resin anion(R.A) 100L are packed in the ion exchange column, be that 1-6m/h is that the hydrochloric acid of 2-6% and aqueous sodium hydroxide solution that the 10-100L massfraction is 2-6% carry out pre-treatment to described resin anion(R.A) with the 10-100L massfraction successively with the linear velocity, be 1-6m/h with the linear velocity again, be that the aqueous sodium hydroxide solution of 2-6% is regenerated to described resin anion(R.A) with the 100-800L massfraction; The regeneration back contains Na with the described resin anion(R.A) of deionized water wash to water outlet
+Content is below 100ppm; With the 100-300L massfraction is the 4-propyl bromide aqueous solution of 5-20%, is that 1-6m/h passes through ion exchange column with the linear velocity, and the TPAOH aqueous solution of collecting the acquisition of exchange back is standby;
(2) molecular sieve is synthetic:
With the 45-180L massfraction is that the TPAOH aqueous solution of 5%-20% is put into reactor, and rotating speed is under the stirring of 50-300 commentaries on classics/min; Tetraethoxy and alcoholic acid mixed solution in the speed adding reactor with 5-50L/h, are continued to stir 10-300min after adding is finished, close kettle cover; Speed with 1-15 ℃/min is warming up to 100-150 ℃, reacted 80-120 hour, reduce to room temperature, gained reaction solution membrane filtering method, with the pH=10-11 removal impurity of deionized water wash to filtrate, after the reaction solution drying behind the removal impurity,, obtain molecular screen primary powder at 500-650 ℃ of following roasting 4-8h; Described TPAOH, tetraethoxy and alcoholic acid mol ratio are 0.5-4: 2-16: 0.1-2;
In the molecular sieve of 40 mass parts, the massfraction that adds the 30-60 mass parts is the silicon sol of 10-25%, the Macrogol 2000 of 0.1-0.3 mass parts, the strong aqua of 10-40 mass parts, the field mountain valley with clumps of trees and bamboo powder of 1-3 mass parts and the active carbon powder of 1-2 mass parts, carries out extruded moulding after mediating with kneader; The gained bar takes out behind 500-650 ℃ of following roasting 4-8h;
Product after the roasting is put into the NH that mass ratio is 2-10: 2-10: 80-96 successively
3-NH
3NO
3-H
2The mixing solutions of O and massfraction be in the hydrofluoric acid aqueous solution of 0.01-0.08% in 80-95 ℃ of following immersion treatment 1-6h, with deionized water wash to the specific conductivity of elutant below 100 μ S/cm; Take out after drying and, take out encapsulation, promptly make a kind of S-1 total silicon molecular sieve once more in 500-650 ℃ of following roasting 4-8h.
2.S-1 the total silicon molecular sieve is characterized in that making with the method for claim 1, described S-1 molecular sieve particle diameter is 100-200nm.
3. the application of the S-1 total silicon molecular sieve of claim 2 in the preparation hexanolactam is characterized in that comprising the steps:
Get and put into reactor, filling with inert gas after 0.1-2g S-1 molecular sieve and 0.7-15g quartz sand mix; Being warming up to 400-550 ℃ of reaction 1-5h, being cooled to 330-390 ℃, under 0.1-0.3MP pressure, will pass through described beds in the presence of rare gas element by the mixing liquid that ammonia, water, cyclohexanone-oxime and methyl alcohol are formed with volume pump, is 1-8h at mass space velocity
-1Under carry out vapor phase beckmann rearrangement reaction and promptly get hexanolactam, keep reaction 200-600h and every the 1h sampling analysis; The mass ratio of ammonia, water, cyclohexanone-oxime and methyl alcohol is 0.006-0.06: 0.5-6: 30-90: 10-70 in the mixing liquid that described ammonia, water, cyclohexanone-oxime and methyl alcohol are formed.
4. application according to claim 3 is characterized in that described rare gas element is argon gas, nitrogen or helium.
5. application according to claim 3 is characterized in that reacted S-1 total silicon molecular sieve is regenerated, and described regenerated condition is: pressure 0.1-0.3MP, temperature 450-650 ℃, volume of air air speed 800-20000h
-1, recovery time 5-30h.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102515193A (en) * | 2011-12-31 | 2012-06-27 | 中国天辰工程有限公司 | Synthetic method of siliceous molecular sieve |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6303099B1 (en) * | 1999-06-30 | 2001-10-16 | Sumitomo Chemical Company, Limited | Process for producing pentacyl-type crystalline zeolites and a process for producing ε-caprolactam using the same |
| CN1415607A (en) * | 2001-10-30 | 2003-05-07 | 中国石油化工股份有限公司 | Method for synthesizing caprolactam |
| CN1883803A (en) * | 2005-06-22 | 2006-12-27 | 中国石油化工股份有限公司 | Process for preparing catalyst for use in preparation of caprolactam from cyclohexanone oxime |
| JP2007222760A (en) * | 2006-02-22 | 2007-09-06 | Sumitomo Chemical Co Ltd | CATALYST FOR PRODUCING epsilon-CAPROLACTAM AND PRODUCTION METHOD OF epsilon-CAPROLACTAM USING THE CATALYST |
| CN101786010A (en) * | 2010-02-09 | 2010-07-28 | 中国天辰工程有限公司 | Catalyst for preparing caprolactam by gas phase Beckmann rearrangement method and preparation method thereof |
-
2010
- 2010-12-30 CN CN201010616382A patent/CN102120589B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6303099B1 (en) * | 1999-06-30 | 2001-10-16 | Sumitomo Chemical Company, Limited | Process for producing pentacyl-type crystalline zeolites and a process for producing ε-caprolactam using the same |
| CN1415607A (en) * | 2001-10-30 | 2003-05-07 | 中国石油化工股份有限公司 | Method for synthesizing caprolactam |
| CN1883803A (en) * | 2005-06-22 | 2006-12-27 | 中国石油化工股份有限公司 | Process for preparing catalyst for use in preparation of caprolactam from cyclohexanone oxime |
| JP2007222760A (en) * | 2006-02-22 | 2007-09-06 | Sumitomo Chemical Co Ltd | CATALYST FOR PRODUCING epsilon-CAPROLACTAM AND PRODUCTION METHOD OF epsilon-CAPROLACTAM USING THE CATALYST |
| CN101786010A (en) * | 2010-02-09 | 2010-07-28 | 中国天辰工程有限公司 | Catalyst for preparing caprolactam by gas phase Beckmann rearrangement method and preparation method thereof |
Cited By (17)
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| CN102515193A (en) * | 2011-12-31 | 2012-06-27 | 中国天辰工程有限公司 | Synthetic method of siliceous molecular sieve |
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| DE102014222018A1 (en) | 2013-10-29 | 2015-04-30 | China Petroleum & Chemical Corporation | Fully formed of Si molecular sieve and synthesis process for it |
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