CN102527424B - After-treatment technology of Beckmann gas-phase rearrangement S-1 full-silica molecular sieve based catalyst - Google Patents
After-treatment technology of Beckmann gas-phase rearrangement S-1 full-silica molecular sieve based catalyst Download PDFInfo
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Abstract
The invention discloses an after-treatment technology of a Beckmann gas-phase rearrangement S-1 full-silica molecular sieve based catalyst, which comprises the following steps of: preparing a mixed solution of strong acid with a certain concentration and hydrofluoric acid in proportion, weighing a certain mass of S-1 full-silica molecular sieve based catalyst and putting into a reactor, measuring out the prepared mixed solution of strong acid and hydrofluoric acid based on the mass of the catalyst and pouring into the reactor, starting stirring, maintaining a certain rotation speed, stopping stirring after reacting for a period of time at room temperature, and washing by using de-ionized water to be neutral. According to the invention, By changing the formula of an S-1 full-silica molecular sieve after-treatment solution and using the mixed solution of strong acid and hydrofluoric acid as an after-treatment solution, the after treatment is carried out at room temperature dropping from about 100 DEG C in conventional processes, the problem that the material of a heat exchanger must be made of an expensive Monel metal due to strong corrosivity of the hydrofluoric acid in the conventional after-treatment process is solved, and equipment cost is substantially saved.
Description
Technical field
The invention belongs to the Preparation of Catalyst field, relate to S-1 total silicon molecular sieve post-treatment new process in a kind of Beckman vapour phase rearrangement synthesis of caprolactam, in particular, relate to a kind of low-cost processes S-1 total silicon molecular sieve technology.
Background technology
Caprolactam is a kind of important chemical material, is the monomer of synthetic nylon 6 and engineering plastics.The process route of synthesis of caprolactam mainly contains two kinds of liquid and gas Beckmann rearrangements at present.On industrial production, mainly be with sulfuric acid catalysis liquid phase rearrangement technology at present.This technology be cyclohexanone oxime under the concentrated sulfuric acid or oleum effect in uniform temperature generation Beckmann rearrangement, utilize the acid caprolactam that generates of ammonia neutralization reaction system then.This technology comparatively maturation, reaction condition mitigation, feed stock conversion and selectivity of product is all higher, but also has a lot of shortcomings.At first the concentrated sulfuric acid 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 (data show 1 ton of caprolactam of every production 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 caprolactam synthesis technique of purpose becomes recent research.Though since the last century the eighties, people have reduced the use of sulfuric acid and the generation of ammonium sulfate by changing reactor types and process conditions, because sulfuric acid uses the problem of generation to be solved always at all.
In order to address the above problem, it is the gas phase beckmann rearrangement production technology of catalyst that people begin one's study with the solid acid.This technology can be avoided the use of sulfuric acid 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 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 conversion ratio and caprolactam are selectively 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 catalyst, at cyclohexanone oxime weight space velocity (WHSV)=2.2h
-1Down, react after 23 hours, the cyclohexanone oxime conversion ratio reduces to 97.9%, and caprolactam selectively only is 81.4%.People are the reaction effect of catalyst in research with the molecular sieve also in addition.For example, J.Catal., 1992,137:252 is catalyst with S-1 total silicon molecular sieve, and the life-span, the cyclohexanone oxime conversion ratio was 90% less than 30h, and caprolactam selectively is 81%.The easy inactivation of catalyst in the above-mentioned research, and caprolactam is selectively not high.
Studies show that, S-1 total silicon molecular sieve catalyst is carried out appropriate postprocessing can significantly improve its reactivity worth.For example, Chinese J.Chem., 2005,26 (5): 417 have reported NH
3-HNO
3Mixed solution can obviously prolong the deactivation rate of S-1 molecular sieve; And Chinese J.Chem., 2006,27 (3): discover S-1 total silicon molecular sieve selectively the significantly improving of caprolactam after 0.04% hydrofluoric acid treatment in 245; USP5403801 has then reported the S-1 total silicon molecular sieve of handling through inorganic alkali solution, at WHSV=8h
-1, reaction 6.25h cyclohexanone oxime conversion ratio is 99.5%, caprolactam selectively is 96.5%, feeding the saturated air that contains methyl alcohol then regenerated 23 hours, after 30 times, the cyclohexanone oxime conversion ratio is 95.3% under the same reaction conditions repeatedly, and caprolactam selectively is 95.3%;
But the condition of in the above-mentioned research S-1 total silicon molecular sieve being carried out the hydrofluoric acid post processing is generally about 100 ℃, need heat hydrofluoric acid solution and will reach this temperature.As everyone knows, hydrofluoric acid has very strong corrosivity, and therefore alternative heat exchanger material is very limited, and monel metal becomes first-selection with its good anti-corrosion usually.But monel metal is very expensive, and its price is up to 1 kilogram in hundreds of unit, is that the heat exchanger cost of material is high with this alloy therefore, how can address this problem the direction that becomes our research.
Summary of the invention
For the problems of the prior art, the invention provides a kind of Beckman vapour phase rearrangement S-1 total silicon molecular sieve catalyst aftertreatment technology, the hydrofluoric acid high temperature corrosion is strong in the solution prior art, and heat exchanger material range of choice is little, uses the high problem of expensive monel metal heat exchanger cost.
The present invention is achieved through the following technical solutions:
A kind of Beckman vapour phase rearrangement S-1 total silicon molecular sieve catalyst aftertreatment technology comprises the steps:
1) preparation of S-1 total silicon molecular sieve aftertreatment fluid
A kind of strong acid is added deionized water be diluted to H
+Concentration is 0.01-0.1mol/l, and hydrofluoric acid is added deionized water, and to be diluted to mass fraction be 0.01-0.2%, and it is standby then these two kinds of solution to be mixed the back with volume ratio 1: 1-3;
Described strong acid is a kind of in hydrochloric acid, sulfuric acid, the nitric acid.
Described strong acid dilution back H
+Concentration is 0.02-0.06mol/l.
Described hydrofluoric acid mass fraction is 0.02-0.16%.
2) S-1 total silicon molecular sieve aftertreatment technology
Take by weighing 40-100g S-1 total silicon molecular sieve catalyst and put into the reactor of polytetrafluoroethylene (PTFE) or polypropylene material, measuring the strong acid for preparing and the mixed solution 200-1000ml of hydrofluoric acid pours in the reactor, open and stir, rotating speed is 50-100r/min, behind reaction 2-6h under the room temperature condition, stop to stir, be washed till neutrality with deionized water; This process is carried out 3 times repeatedly, after reaction is finished, with S-1 total silicon molecular sieve oven dry, with 500-650 ℃ of following roasting 3-6h, get final product S-1 total silicon molecular sieve catalyst product.
Described room temperature condition is 25 ℃.
How to prepare S-1 total silicon molecular sieve and do not belong to claim scope of the present invention.Content involved in the present invention is to reach the purpose of at ambient temperature S-1 total silicon molecular sieve being carried out post processing at S-1 total silicon molecular sieve post processing category treatment technology different from the past.More particularly, the temperature conditions that utilizes hydrofluoric acid containing solution to carry out post processing to S-1 total silicon molecular sieve in the past is about 100 ℃, and this has just caused chooses difficulty to the heat exchanger material in the hydrofluoric acid solution heating process.The present invention has improved the prescription of S-1 total silicon molecular sieve post-treatment solution by research, and last handling process can be carried out at ambient temperature, need not it is heated, and therefore obviously provides cost savings.
The post-processing approach advantage of S-1 total silicon molecular sieve of the present invention is:
1) the present invention uses the mixed solution of strong acid and hydrofluoric acid as aftertreatment fluid by improving the prescription of S-1 total silicon molecular sieve post-treatment solution, makes its post-processing temperature is reduced under the room temperature condition and can carries out by about 100 ℃ in the technology in the past.The present invention has fundamentally solved in the past in the aftertreatment technology because the severe corrosive of hydrofluoric acid, and the heat exchanger material must be selected the problem of expensive monel metal for use, saved equipment cost significantly.
2) since among the present invention post-processing temperature be room temperature condition, therefore significantly reduced in the aftertreatment technology the consumption of energy, meet the developing direction of national energy-saving and emission-reduction.
The specific embodiment
The present invention is further illustrated below in conjunction with specific embodiment.In following embodiment and comparative example, evaluating catalyst adopts following method:
Get and put into reactor formation beds, inflated with nitrogen after 0.5g S-1 total silicon molecular sieve and 5g quartz sand mix; Being warming up to 550 ℃ of reaction 4h, being cooled to 340 ℃, with measuring pump the cyclohexanone oxime methanol solution of mass fraction 40% is injected described beds, is 4h at the cyclohexanone oxime mass space velocity
-1Under carry out vapor phase beckmann rearrangement reaction and namely get caprolactam, keep reaction 40h, the product sample analysis of every 10h 1 time.
Following example has comprised the comparative example of embodiment and embodiment.Wherein embodiment is the evaluation result of the S-1 total silicon molecular sieve catalyst for preparing under the catalyst post-treatment condition in claim scope of the present invention that carries out in order to prove validity of the present invention; Comparative example is the S-1 total silicon molecular sieve catalyst that adopts existing aftertreatment technology preparation.
Embodiment 1:
Hydrochloric acid is added deionized water, and to be diluted to H+ concentration be 0.02mol/l, and hydrofluoric acid is added deionized water, and to be diluted to mass fraction be 0.02%, and it is standby then these two kinds of solution to be mixed the back with volume ratio at 1: 3.
Take by weighing 40g S-1 total silicon molecular sieve catalyst and put into the reactor of polytetrafluoroethylene (PTFE) or polypropylene material, measuring the strong acid for preparing and the mixed solution 200ml of hydrofluoric acid pours in the reactor, open and stir, rotating speed is 50r/min, behind reaction 2h under the room temperature condition, stop to stir, be washed till neutrality with deionized water.This process is carried out 3 times repeatedly.After reaction is finished, with S-1 total silicon molecular sieve oven dry, in 500 ℃ of following roasting 3h, get final product S-1 total silicon molecular sieve catalyst product.
The evaluating catalyst of S-1 total silicon molecular sieve gas phase beckmann rearrangement synthesis of caprolactam the results are shown in Table 1.
Embodiment 2:
Sulfuric acid is added deionized water be diluted to H
+Concentration is 0.03mol/l, and hydrofluoric acid is added deionized water, and to be diluted to mass fraction be 0.06%, and it is standby then these two kinds of solution to be mixed the back with volume ratio at 1: 2.
Take by weighing 60g S-1 total silicon molecular sieve catalyst and put into the reactor of polytetrafluoroethylene (PTFE) or polypropylene material, measuring the strong acid for preparing and the mixed solution 400ml of hydrofluoric acid pours in the reactor, open and stir, rotating speed is 80r/min, behind reaction 3h under the room temperature condition, stop to stir, be washed till neutrality with deionized water.Then under the same conditions, this reaction is carried out 3 times repeatedly.After reaction is finished, with S-1 total silicon molecular sieve oven dry, in 550 ℃ of following roasting 4h, get final product S-1 total silicon molecular sieve catalyst product.
The evaluating catalyst of S-1 total silicon molecular sieve gas phase beckmann rearrangement synthesis of caprolactam the results are shown in Table 1.
Embodiment 3:
Hydrochloric acid is added deionized water be diluted to H
+Concentration is 0.05mol/l, and hydrofluoric acid is added deionized water, and to be diluted to mass fraction be 0.1%, and it is standby then these two kinds of solution to be mixed the back with volume ratio at 1: 1.
Take by weighing 80g S-1 total silicon molecular sieve catalyst and put into the reactor of polytetrafluoroethylene (PTFE) or polypropylene material, measuring the strong acid for preparing and the mixed solution 800ml of hydrofluoric acid pours in the reactor, open and stir, rotating speed is 100r/min, behind reaction 4h under the room temperature condition, stop to stir, be washed till neutrality with deionized water.This process is carried out 3 times repeatedly.After reaction is finished, with S-1 total silicon molecular sieve oven dry, in 600 ℃ of following roasting 5h, get final product S-1 total silicon molecular sieve catalyst product.
The evaluating catalyst of S-1 total silicon molecular sieve gas phase beckmann rearrangement synthesis of caprolactam the results are shown in Table 1.
Embodiment 4:
Nitric acid is added deionized water, and to be diluted to H+ concentration be 0.06mol/l, and hydrofluoric acid is added deionized water, and to be diluted to mass fraction be 0.16%, and it is standby then these two kinds of solution to be mixed the back with volume ratio at 1: 1.
Take by weighing 100g S-1 total silicon molecular sieve catalyst and put into the reactor of polytetrafluoroethylene (PTFE) or polypropylene material, measuring the strong acid for preparing and the mixed solution 1000ml of hydrofluoric acid pours in the reactor, open and stir, rotating speed is 100r/min, behind reaction 6h under the room temperature condition, stop to stir, be washed till neutrality with deionized water.This process is carried out 3 times repeatedly.After reaction is finished, with S-1 total silicon molecular sieve oven dry, in 650 ℃ of following roasting 6h, get final product S-1 total silicon molecular sieve catalyst product.
The evaluating catalyst of S-1 total silicon molecular sieve gas phase beckmann rearrangement synthesis of caprolactam the results are shown in Table 1.
Embodiment 5:
Nitric acid is added deionized water be diluted to H
+Concentration is 0.02mol/l, and hydrofluoric acid is added deionized water, and to be diluted to mass fraction be 0.04%, and it is standby then these two kinds of solution to be mixed the back with volume ratio at 1: 2.
Take by weighing 70g S-1 total silicon molecular sieve catalyst and put into the reactor of polytetrafluoroethylene (PTFE) or polypropylene material, measuring the strong acid for preparing and the mixed solution 900ml of hydrofluoric acid pours in the reactor, open and stir, rotating speed is 90r/min, behind reaction 4h under the room temperature condition, stop to stir, be washed till neutrality with deionized water.This process is carried out 3 times repeatedly.After reaction is finished, with S-1 total silicon molecular sieve oven dry, in 550 ℃ of following roasting 5h, get final product S-1 total silicon molecular sieve catalyst product.
The evaluating catalyst of S-1 total silicon molecular sieve gas phase beckmann rearrangement synthesis of caprolactam the results are shown in Table 1.
Comparative example:
Take by weighing 40g S-1 total silicon molecular sieve catalyst and put into reactor, add the hydrofluoric acid solution of 600ml mass fraction 0.06%, open and stir, rotating speed is 50r/min, speed with 6 ℃/min is warming up to 100 ℃, keeps to stop behind the 2h stirring, and is washed till neutrality with deionized water.This process is carried out 3 times repeatedly.After reaction is finished, with S-1 total silicon molecular sieve oven dry, in 500 ℃ of following roasting 3h, get final product S-1 total silicon molecular sieve catalyst product.
The evaluating catalyst of S-1 total silicon molecular sieve gas phase beckmann rearrangement synthesis of caprolactam the results are shown in Table 1.
The present invention can realize post processing under the room temperature condition of S-1 total silicon molecular sieve, thoroughly solves in the post-treatment solution owing to contain the etching problem that hydrofluoric acid brings.The embodiment that the invention is not restricted to mention in the literary composition, above-described embodiment only is used for the proof applicability, not deviating from the essence that the present invention is disclosed and describe, does not exceed under the situation of claim scope, can select corresponding post-treatment condition according to the disclosed content of specification.
Claims (4)
1. a Beckman vapour phase rearrangement S-1 total silicon molecular sieve catalyst aftertreatment technology is characterized in that comprising the steps:
1) preparation of S-1 total silicon molecular sieve aftertreatment fluid
A kind of strong acid is added deionized water be diluted to H
+Concentration is 0.01-0.1mol/l, and hydrofluoric acid is added deionized water, and to be diluted to mass fraction be 0.01-0.2%, and it is standby then these two kinds of solution to be mixed the back with volume ratio 1:1-3;
2) S-1 total silicon molecular sieve aftertreatment technology
Take by weighing 40-100gS-1 total silicon molecular sieve catalyst and put into the reactor of polytetrafluoroethylene (PTFE) or polypropylene material, measuring the strong acid for preparing and the mixed solution 200-1000ml of hydrofluoric acid pours in the reactor, open and stir, rotating speed is 50-100r/min, behind reaction 2-6h under the room temperature condition, stop to stir, be washed till neutrality with deionized water; This process is carried out 3 times repeatedly, after reaction is finished, with S-1 total silicon molecular sieve oven dry, with 500-650 ℃ of following roasting 3-6h, get final product S-1 total silicon molecular sieve catalyst product;
Described strong acid is a kind of in hydrochloric acid, sulfuric acid, the nitric acid.
2. S-1 total silicon molecular sieve catalyst aftertreatment technology according to claim 1 is characterized in that described strong acid dilution back H+ concentration is 0.02-0.06mol/l.
3. S-1 total silicon molecular sieve catalyst aftertreatment technology according to claim 1 is characterized in that described hydrofluoric acid mass fraction is 0.02-0.16%.
4. S-1 total silicon molecular sieve catalyst aftertreatment technology according to claim 1 is characterized in that described room temperature condition is 25 ℃.
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| CN108080027B (en) * | 2017-12-23 | 2021-05-28 | 中国天辰工程有限公司 | Resin catalyst treatment process for preparing caprolactam through liquid phase Beckmann rearrangement |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4359587A (en) * | 1980-09-22 | 1982-11-16 | Mirkhasil Abdurakhmanov | Method for preparing carbonyl compounds |
| CN102120589A (en) * | 2010-12-30 | 2011-07-13 | 中国天辰工程有限公司 | S-1 full-silicon molecular sieve and preparation method thereof as well as application of S-1 full-silicon molecular sieve in caprolactam preparation |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4359587A (en) * | 1980-09-22 | 1982-11-16 | Mirkhasil Abdurakhmanov | Method for preparing carbonyl compounds |
| CN102120589A (en) * | 2010-12-30 | 2011-07-13 | 中国天辰工程有限公司 | S-1 full-silicon molecular sieve and preparation method thereof as well as application of S-1 full-silicon molecular sieve in caprolactam preparation |
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