CN109433230A - A kind of preparation method for the solid acid-base bifunctional catalyst preparing salicylonitrile for salicylamide dehydration - Google Patents
A kind of preparation method for the solid acid-base bifunctional catalyst preparing salicylonitrile for salicylamide dehydration Download PDFInfo
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- CN109433230A CN109433230A CN201811316996.1A CN201811316996A CN109433230A CN 109433230 A CN109433230 A CN 109433230A CN 201811316996 A CN201811316996 A CN 201811316996A CN 109433230 A CN109433230 A CN 109433230A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/30—Ion-exchange
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/20—Preparation of carboxylic acid nitriles by dehydration of carboxylic acid amides
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Abstract
The invention belongs to catalyst fields, and in particular to a kind of solid acid-base bifunctional catalyst that salicylonitrile is prepared for salicylamide dehydration further relates to the preparation method of above-mentioned catalyst.The solid catalyst includes Zr (NO3)4·5H2O and montmorillonite, the Zr (NO3)4·5H2O and the montmorillonite carrier through peracid treatment are combined catalyst SO4 2‑/Zr(SO4)2/ montmorillonite.SO4 2‑/Zr(SO4)2/ montmorillonite catalyst has the strong acid site B and weak B alkali center, two activated centres of B acid and B alkali, which can act synergistically, during being catalyzed dehydration of amide forms the intermediates of hexatomic ring with amide, the activation energy for reducing reaction, making entirely to react can go on smoothly at a lower temperature.SO4 2‑/Zr(SO4)2/ montmorillonite catalyst, which prepares salicylonitrile reaction for salicylamide dehydration, to be had the advantages that high activity, high stability, convenient separation, is easily recycled, environmental-friendly, and cheap is easy to large-scale production.
Description
Technical field
The invention belongs to catalyst fields, and in particular to a kind of difunctional as modified zirconia and one kind made of montmorillonite Composite
The preparation method of solid catalyst.
Background technique
Dehydration is the important method that amides compound directly prepares cyano-containing fine chemicals.Amides at present
The dehydration technique for closing object is substantially using toluene or chlorobenzene as solvent, with phosgene, thionyl chloride etc. for dehydrating agent.It is used
These dehydrating agents have it is expensive, have severe toxicity, using hyperstoichiometry, post-processing is difficult, environmental pollution is serious the defects of;
And increasingly drawn attention with the catalytic and dehydration reaction that solid catalyst carries out, because solid catalyst and reactant are in not
Same phase, lock out operation are easy, recyclable and reuse, and without equipment corrosion and the problems such as environmental pollution.
The report in patent (US6248917 B1) such as Wolfgang uses phosphoric acid load silica gel catalysis of solid catalyst acyl
Amine dehydration prepares nitrile, is in high vacuum conditions, the salicylamide continuously and smoothly of molten condition to be inputted gas phase fixed bed and is carried out
Dehydration prepares nitrile;The optimum temperature of the reaction process is 390 DEG C, and reaction temperature is excessively high in practical applications, and it is larger to consume energy,
Its poor repeatability, loss of active component are fast, can generate a large amount of phosphorus-containing wastewater, it is difficult to handle.
Jorg is using toluene as solvent, and Acket is reacted with excess phosgene, after adding water to be azeotroped off excess phosgene
Crystallization obtains product, and yield is up to 94%.The technique is using phosgene as dehydrating agent, although yield is higher, phosgene is severe toxicity,
It is difficult to operate in production, risk is larger;It is also accompanied by a large amount of hydrogen chloride gas simultaneously to generate, environmental pollution is serious.
Therefore, for above-mentioned defect, need to design that a kind of activity is high, reproducible and loss of active component is slow and has
There is preferable stability, convenient for separation, Yi Huishou, environmentally friendly, the low catalyst of reaction temperature, to further decrease life
Produce cost.
Summary of the invention
It is an object of the invention to solve existing catalyst for dehydration of amide prepare nitrile when activity is low, reaction temperature is high,
The problem of poor repeatability, while inconvenient to prior art, develop it is a kind of it is easy to operate, have compared with low reaction temperatures, higher
Amide conversion ratio and nitrile selectivity difunctional solid catalyst and preparation method thereof.
Difunctional solid catalyst includes SO4 2-/ZrO2And montmorillonite, the solid catalyst are Zr (NO3)4·5H2O
Compound ZrO is made with the montmorillonite carrier through peracid treatment2/ montmorillonite impregnates the compound with acid solution, final to be made
SO4 2-/ZrO2The difunctional solid catalyst of/montmorillonite.
The difunctional solid catalyst, the content of zirconium are the 5-20% of montmorillonite quality.
The difunctional solid catalyst, acid processing acid solution used is sulfuric acid solution or hydrochloric acid solution.
The preparation method of the difunctional solid catalyst, includes the steps that following:
A. a certain amount of montmorillonite is weighed, is added in 3-6mol/L acid solution, is acidified 4h at 100 DEG C, is taken out after solution is cooling
Filter, is washed to neutrality for montmorillonite, dries at 150 DEG C to constant weight and obtains montmorillonite carrier.
The ratio of the montmorillonite and acid solution are as follows: montmorillonite: acid solution=1g:10g;
B. by montmorillonite carrier obtained in step a and Zr (NO3)4·5H2O is add to deionized water;Then concentrated ammonia liquor is added dropwise
The Ph value for adjusting solution is 9-11;Flow back 30min at 70-100 DEG C;And it is aged 12h with this condition, it then filters, washes,
Separation, the solid isolated dry 4-6h at 100-120 DEG C, by obtained solid grind into powder.
Above-mentioned each component mass ratio are as follows: Zr (NO3)4·5H2O: montmorillonite=1-2:2-2.5, montmorillonite: deionized water=1-
3g:10-20ml。
C. certain density sulfuric acid solution is configured, powder obtained in step b is added in the solution, is impregnated at room temperature
About 6-8h is filtered, and drying for 24 hours, then calcines 5-8h under conditions of 450-650 DEG C under the conditions of 100-120 DEG C.
The concentration of above-mentioned sulfuric acid solution is 0.5-1mol/L, and the amount ratio of solid powder and solution is 1g:5ml.
Montmorillonite carrier used in the present invention has the stratiform of two layers Si-O tetrahedron (T) and one layer of Al-O octahedron (O)
Structure, the polymerization or oligomeric hydroxy metal cation that zirconates is hydrolyzed into can be exchanged with the cation between cheating engaging layer;
To play good load effect to zirconium ion, the loss of active component in reaction process, ZrO can be effectively reduced2Itself is not
With stronger acid centre, and impregnated by sulfuric acid solution, after calcining, the Zr containing Severe Power Shortage4+, can be with sulfate radical
In oxygen atom form stronger coordinate bond, while sulfur-to-oxygen double bond has stronger inductive effect, so that Zr4+Electropositive is reinforced,
To form stronger L acid centre;In the Zr-O key being formed simultaneously, the electronegativity of oxygen atom is greater than the electronegativity of zirconium atom,
Charge density is higher around oxygen atom, so that oxygen atom is in certain alkalescent (B alkali);Have just because of the catalyst relatively strong
The acid site B and weak B alkali center coexist, during being catalyzed dehydration of amide can with amide formed hexatomic ring intermediate mistake
State is crossed, the activation energy of reaction is reduced, making entirely to react can go on smoothly at a lower temperature;Catalyst is easy after reaction
It can reuse in separation and again.
Detailed description of the invention
Fig. 1 is SO4 2-/Zr(SO4)2/ montmorillonite catalyst salicylamide dehydration preparation fine reaction evaluating the figure of bigcatkin willow.
Specific embodiment
Embodiment 1
200ml, 5molL is added in montmorillonite 20g after taking high temperature drying to remove water-1Sulfuric acid solution in, under the conditions of 100 DEG C
It is acidified 4h, filters, is washed to neutrality, 150 DEG C of dryings are spare to constant weight.
Montmorillonite, five water zirconium nitrate (Zr(NO of 6.4g after taking 10g to be dried3)4·5H2O),
It is added in 150ml deionized water, stirring is uniformly mixed it, and 25% ammonium hydroxide is added dropwise under conditions of 70 DEG C, adjusts solution
Ph value is 9, stirs 30min;Then it is aged 12h;It filters, washing, separation, the solid isolated dry 6h at 110 DEG C;By institute
Solid abrasive is obtained into powder.
The sulfuric acid solution for configuring 30ml, 0.5mol/L, powder obtained in previous step is added in the solution prepared, room
Temperature is lower to impregnate 7h, filters, dry under the conditions of 110 DEG C that 6h is then calcined under conditions of 500 DEG C for 24 hours, and SO is made4-/ZrO2/
Montmorillonite catalyst.
In the reaction unit of the three-necked flask equipped with magneton stirring, water segregator, reflux condensing tube and thermometer, it is added
103g toluene (toluene is solvent and water entrainer), 21g salicylamide, 6.3gSO4 2-/ZrO2/ montmorillonite flows back at 110 DEG C
6h.During the reaction, toluene takes the water of generation out of, into water segregator.In water segregator, water is immiscible with toluene, stands
Water is released by lower part after layering.After the completion of dehydration, solid catalyst is separated through filtering, and residual reaction liquid has been cooled to room temperature
Crystal is precipitated, using filtering to isolate crude product;Resulting crude product is recrystallized with toluene, to obtain finished product.
According to gas chromatographic analysis, reaction result is as shown in Figure 1.
Test of many times react and is basically completed after obtaining reaction 4h with this condition, and follow-up test unifies the reaction time as 4h.
Embodiment 2
By 1 250 DEG C of high-temperature process 8h of filtered catalyst of embodiment, sufficiently to dry reactant remaining in catalyst system
Equal liquid impurities.Weighing dry rear catalyst weight is 6.28g, and the total number of dropouts of catalyst is 0.3%, this loss is negligible,
Then second of recycling is carried out again.
Salicylamide dehydration evaluation procedure is same as above, and reaction result is as shown in Figure 1.
Embodiment 3
The recovery method and evaluation condition of catalyst are with embodiment 2, except that catalyst third time huge profit is used, reaction result
See Fig. 1.
Embodiment 4
The recovery method and evaluation condition of catalyst are with embodiment 2, except that the 4th huge profit of catalyst is used, reaction result
See Fig. 1.
Embodiment 5
The recovery method and evaluation condition of catalyst are with embodiment 2, except that the 5th huge profit of catalyst is used, reaction result
See Fig. 1.
Embodiment 6
Method for preparing catalyst and evaluation condition are with embodiment 1, except that acid handles salt used in catalyst preparation process
Acid solution is 5 molL-1。
Embodiment 7
Method for preparing catalyst and evaluation condition are with embodiment 1, except that in catalyst preparation process, Zr (NO3)4 ·
5H2O: montmorillonite=4:5, reaction result are shown in Fig. 1.
Embodiment 8
Method for preparing catalyst and evaluation condition are with embodiment 1, except that in catalyst preparation process, Zr (NO3)4 ·
5H2O: montmorillonite=2:5, reaction result are shown in Fig. 1.
Embodiment 9
Method for preparing catalyst and evaluation condition are with embodiment 1, except that in catalyst preparation process, Zr (NO3)4 ·
5H2O: montmorillonite=2:4, reaction result are shown in Fig. 1.
Embodiment 10
Method for preparing catalyst and evaluation condition are with embodiment 1, except that in catalyst preparation process, digestion time is
8h, reaction result are shown in Fig. 1.
Embodiment 11
Method for preparing catalyst and evaluation condition are with embodiment 1, except that in catalyst preparation process, digestion time is
10h, reaction result are shown in Fig. 1.
Embodiment 12
Method for preparing catalyst and evaluation condition are with embodiment 1, except that in catalyst preparation process, digestion time is
14h, reaction result are shown in Fig. 1.
Embodiment 13
Method for preparing catalyst and evaluation condition are with embodiment 1, except that in catalyst preparation process, maturing temperature is
600 DEG C, calcining time 2h, reaction result is shown in Fig. 1.
Embodiment 14
Method for preparing catalyst and evaluation condition are with embodiment 1, except that in catalyst preparation process, maturing temperature is
550 DEG C, calcining time 3h, reaction result is shown in Fig. 1.
Embodiment 15
Method for preparing catalyst and evaluation condition are with embodiment 1, except that in catalyst preparation process, maturing temperature is
550 DEG C, calcining time 4h, reaction result is shown in Fig. 1.
Embodiment 16
Method for preparing catalyst and evaluation condition are with embodiment 1, except that in catalyst preparation process, maturing temperature is
450 DEG C, calcining time 5h, reaction result is shown in Fig. 1.
Embodiment 17
Method for preparing catalyst and evaluation condition are with embodiment 1, except that in catalyst preparation process, maturing temperature is
400 DEG C, calcining time 6h, reaction result is shown in Fig. 1.
Embodiment 18
Method for preparing catalyst and evaluation condition are with embodiment 1, except that in catalyst preparation process, maturing temperature is
350 DEG C, calcining time 8h, reaction result is shown in Fig. 1.
The catalyst activity is higher it can be seen from figure 1 above, and after recycling five times, activity is still higher, repeats
Good, the recoverable of property;Find out from the comparison of embodiment 6 and 1, acid handles acid solution preferably sulfuric acid solution used;Embodiment 7-9
1 it can be seen that the Zr (NO in catalyst preparation process in conjunction with the embodiments3)4·5H2O: montmorillonite=2:4 excellent catalytic effect,;
Embodiment 10-12 1 show that digestion time is preferably 10-14h in catalyst preparation process in conjunction with the embodiments;Embodiment 13-18 knot
It closes embodiment 1 and show that maturing temperature is preferably 500-550 DEG C in catalyst preparation process, calcining time is preferably 3-4h.
Claims (8)
1. a kind of solid acid-base bifunctional catalyst, it is characterised in that: the solid catalyst includes Zr (NO3)4·5H2O and
Montmorillonite, the catalyst is by Zr (NO3)4·5H2O and the montmorillonite carrier through peracid treatment are compound using dipping, roasting
It is made.
2. difunctional solid catalyst according to claim 1, it is characterised in that: the content of zirconium is to cover in the catalyst
The 5-20% of de- soil property amount.
3. difunctional solid catalyst according to claim 1, it is characterised in that: acid processing acid solution used is sulfuric acid
Solution or hydrochloric acid solution.
4. the preparation method of difunctional solid catalyst according to claim 1, includes the steps that following:
A. it weighs a certain amount of montmorillonite to be added in the acid solution of 3-6mol/L, is acidified 4h at 100 DEG C, taken out after solution is cooling
Filter, is washed to neutrality for montmorillonite, dries at 150 DEG C to constant weight and obtains montmorillonite carrier, the ratio of montmorillonite and acid solution
Are as follows: montmorillonite: acid solution=1g:10g;
B. by montmorillonite carrier obtained in step a and Zr (NO3)4·5H2O is add to deionized water, and concentrated ammonia liquor is then added dropwise
The Ph value for adjusting solution is 9-11;Flow back 30min at 70-100 DEG C;And it is aged 12h with this condition, it then filters, washes,
Separation, the solid isolated dry 4-6h at 100-120 DEG C, by obtained solid grind into powder, each component mass ratio are as follows: Zr
(NO3)4·5H2O: montmorillonite=1-2:2-5, montmorillonite: deionized water=1-3g:10-20ml;
C. certain density sulfuric acid solution is configured, powder obtained in step b is added in the solution, impregnates about 6- at room temperature
8h is filtered, dry under the conditions of 100-120 DEG C then to calcine 5-8h under conditions of 450-650 DEG C for 24 hours, sulfuric acid solution it is dense
Spending is 0.5-1mol/L, and the amount ratio of solid powder and solution is 1g:5ml.
5. the preparation method of difunctional solid catalyst according to claim 4, it is characterised in that: acid described in step a
Solution is 5molL-1Sulfuric acid it is molten.
6. the preparation method of difunctional solid catalyst according to claim 4, it is characterised in that: done in the step b
Dry temperature is 110-120 DEG C, and calcination temperature is 500-600 DEG C in the step c, calcining time 6-8h.
7. the preparation method of difunctional solid catalyst according to claim 4, it is characterised in that: each in the step b
Constituent mass ratio is Zr (NO3)4·5H2O: montmorillonite=1:2.5, montmorillonite: deionized water=1g:10ml.
8. the preparation method of difunctional solid catalyst according to claim 4, it is characterised in that: dripped in the step b
Adding ammonium hydroxide to adjust the ph value of solution is 9-10.
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115518671A (en) * | 2021-06-24 | 2022-12-27 | 中国石油化工股份有限公司 | Catalyst for preparing phthalonitrile and preparation method and application thereof |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1613559A (en) * | 2004-09-28 | 2005-05-11 | 北京化工大学 | Preparation for hydrophobic solid acid catalyst |
CN101126032A (en) * | 2007-09-29 | 2008-02-20 | 华中农业大学 | Method for preparing biological diesel oil by using solid acid base double-function catalyst |
CN101869847A (en) * | 2010-06-28 | 2010-10-27 | 济南大学 | Micro-spherical polymer solid acid esterification catalyst and preparation method thereof |
KR20130136312A (en) * | 2012-06-04 | 2013-12-12 | 지에스칼텍스 주식회사 | Preparing method of biodegradable ester base oil using solid acid catalyst |
CN105396602A (en) * | 2015-11-06 | 2016-03-16 | 济南同誉新材料科技有限公司 | Composite solid acid catalyst, and preparation method and regeneration method thereof |
CN105665015A (en) * | 2016-01-13 | 2016-06-15 | 济南大学 | Solid acid catalyst, preparation method and application thereof |
CN106311345A (en) * | 2016-07-25 | 2017-01-11 | 江苏大学 | Acid-base bifunctional solid catalyst and preparation method thereof |
-
2018
- 2018-11-07 CN CN201811316996.1A patent/CN109433230A/en active Pending
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1613559A (en) * | 2004-09-28 | 2005-05-11 | 北京化工大学 | Preparation for hydrophobic solid acid catalyst |
CN101126032A (en) * | 2007-09-29 | 2008-02-20 | 华中农业大学 | Method for preparing biological diesel oil by using solid acid base double-function catalyst |
CN101869847A (en) * | 2010-06-28 | 2010-10-27 | 济南大学 | Micro-spherical polymer solid acid esterification catalyst and preparation method thereof |
KR20130136312A (en) * | 2012-06-04 | 2013-12-12 | 지에스칼텍스 주식회사 | Preparing method of biodegradable ester base oil using solid acid catalyst |
CN105396602A (en) * | 2015-11-06 | 2016-03-16 | 济南同誉新材料科技有限公司 | Composite solid acid catalyst, and preparation method and regeneration method thereof |
CN105665015A (en) * | 2016-01-13 | 2016-06-15 | 济南大学 | Solid acid catalyst, preparation method and application thereof |
CN106311345A (en) * | 2016-07-25 | 2017-01-11 | 江苏大学 | Acid-base bifunctional solid catalyst and preparation method thereof |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115518671A (en) * | 2021-06-24 | 2022-12-27 | 中国石油化工股份有限公司 | Catalyst for preparing phthalonitrile and preparation method and application thereof |
CN115518671B (en) * | 2021-06-24 | 2024-01-26 | 中国石油化工股份有限公司 | Catalyst for preparing phthalonitrile, preparation method and application thereof |
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Application publication date: 20190308 |