CN101856608A - Catalyst for synthesizing acetonitrile by using acetic acid and ammonia and manufacturing method thereof - Google Patents
Catalyst for synthesizing acetonitrile by using acetic acid and ammonia and manufacturing method thereof Download PDFInfo
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- CN101856608A CN101856608A CN200910066827A CN200910066827A CN101856608A CN 101856608 A CN101856608 A CN 101856608A CN 200910066827 A CN200910066827 A CN 200910066827A CN 200910066827 A CN200910066827 A CN 200910066827A CN 101856608 A CN101856608 A CN 101856608A
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- catalyst
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- solid acid
- acetonitrile
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Abstract
The invention relates to the field of chemical catalyst preparation, and discloses a catalyst for synthesizing acetonitrile by using acetic acid and ammonia and a manufacturing method thereof. The catalyst comprises the following substances in percentage by weight: 85 to 90 percent of gamma-Al2O3, 1 to 5 percent of K2MoO4 or H3PMo12O4, 1 to 3 percent of KNO3, 3 to 8 percent of solid acid and 2 to 6 percent of NaSiO3. The catalyst is prepared by the steps of mixing and stirring, curing, granulating, roasting, cooling and the like. Because the catalyst is adopted in the process of synthesizing the acetonitrile by using the acetic acid and the ammonia, the reaction temperature is reduced, the conversion rate of the acetic acid is improved, the selectivity of the acetonitrile is improved and the economic benefit is improved.
Description
Technical field
The invention belongs to the chemical catalyst preparation field, be used in the catalyst in acetate and the ammonia synthesis acetonitrile process and the manufacture method of this catalyst specifically.
Background technology
At present the production method of acetonitrile is a lot, and it is that the by-product of going back of producing acetonitrile is an acetonitrile that direct purpose is arranged.But adopt following two kinds of methods usually, one, ethanol ammoniation process: C
2H
5OH+NH
3=CH
3CN+H
2O+H
2This method is because of the many separation difficulty of byproduct, and catalyst preparation technology do not pass a test, and do not realize industrialization.Its two, acetate ammoniation process: CH
3COOH+NH
3=CH
3CN+2H
2O; It is good that acetate and ammonia react make the acetonitrile quality, and the domestic market adopts this method to produce acetonitrile.But this reaction temperature height, acetate consumption is big, and economic benefit is relatively poor.
Summary of the invention
The objective of the invention is provides a kind of high activity, catalysts selective in acetate and ammonia synthesis acetonitrile process, reaction temperature is reduced, and improves the acetate conversion ratio, improves the acetonitrile selectivity.
The object of the present invention is achieved like this,
This is used for the catalyst of acetate and ammonia synthesis acetonitrile, and each substance weight percentage composition is:
γ-Al
2O
385-90% K
2MoO
4Or H
3PMo
12O
401-5%
KNO
31-3% solid acid 3-8% NaSiO
32-6%.
Containing Zr in the described solid acid, is benchmark with the weight of this catalyst, the weight percentage 2-6% of Zr.
Make the method for above-mentioned catalyst:
A, with γ-Al
2O
3, K
2MoO
4, KNO
3, solid acid and NaSiO
3Add in proportion in the agitator, add deionized water and a certain amount of CMC simultaneously, stir into thick;
B, with the mixture of viscous form slaking;
C, with the slaking mixture with extruder granulation and oven dry;
D, will dry catalyst muffle furnace roasting;
Catalyst cooling room temperature after e, the roasting promptly obtains catalyst of the present invention.
Solid acid manufacture method described in the last step is as follows: in proportion with ZrOCl
28H
2O and Al
2(SO
4)
38H
2O is dissolved in the deionized water, two kinds of solution is mixed again, and regulates pH value between 8-9 with ammoniacal liquor, must precipitate, and gained is precipitated ageing was filtered after 12 hours, drying, is the H of 1-10% with concentration
2SO
4Soaked 40 minutes, and after filtration, the drying, under 450 ℃ of conditions, obtained solid acid in 6 hours with the muffle furnace roasting.
Described ZrOCl
28H
2O and Al
2(SO
4)
38H
2The O mol ratio is 1: 1.
Weight with this catalyst is benchmark, and the CMC weight percentage is 1.5% among the described step a.
The curing time is 30-60 minute among the described step b.
Described step c extruding pelletization granularity is 2.5-5mm, bake out temperature 30-150 ℃, and 3 hours time.
Described steps d sintering temperature is 450-480 ℃, and the time is 10-20 hour.
Adopt above-mentioned catalyst to make in acetate and ammonia synthesis acetonitrile process, reduce reaction temperature, improve the acetate conversion ratio, improve the acetonitrile selectivity, increase economic efficiency.
The specific embodiment
This is used for the catalyst of acetate and ammonia synthesis acetonitrile, and each substance weight percentage composition is:
γ-Al
2O
385-90% K
2MoO
4Or H
3PMo
12O
401-5%
KNO
31-3% solid acid 3-8% NaSiO
32-6%.
This method for preparing catalyst comprises the steps:
1, at first preparing solid acid, is 1: 1 ZrOCl with mol ratio
28H
2O and Al
2(SO
4)
316H
2In the O dissolving deionized water, regulate pH value between 8-9, must precipitate with ammoniacal liquor.Precipitation through ageing filter after 12 hours, drying, be 1-10%H with concentration
2SO
4Soaked 40 minutes, and after filtration, the drying, under 450 ℃ of conditions, obtained solid acid in 6 hours with the muffle furnace roasting.
2, with γ-Al
2O
3, K
2MoO
4(or H
3PMo
12O
40), KNO
3, solid acid, NaSiO
3(waterglass) and weight percentage are that 1.5% CMC adds in the agitator in proportion, add deionized water and stirring simultaneously and become thick;
3, with mixture of viscous form slaking 30-60 minute;
4, with the slaking mixture with extruder granulation and bake out temperature 30-150 ℃, 3 hours time;
5, the catalyst after will drying is calcined with muffle furnace; Calcining heat is 450-480 ℃; Time is 10-20 hour;
6, the cooling of the catalyst after roasting room temperature promptly obtains catalyst of the present invention.
Embodiment
Embodiment 1: get 63 gram Al
2(SO
4)
316H
2O and 32.2 gram ZrOCl
28H
2O is dissolved in the 200ml deionized water, adds ammoniacal liquor and regulates pH between 8-9, has precipitation behind the adding ammoniacal liquor and separates out.Precipitation through ageing filter after 12 hours, drying, with the H of the 100ml degree of depth 5%
2SO
4Soaked 40 minutes, and after filtration, the drying, under 450 ℃ of conditions, obtained solid acid 37 grams in 6 hours with the muffle furnace roasting.
Take by weighing 90 gram γ-Al respectively
2O
3, 1.5 the gram K
2MoO
4, 1 the gram KNO
3, 3 the gram solid acids, 4 the gram NaSiO
3(liquid) adds in the 500ml beaker that 80 gram deionized waters are housed, and adds 3 gram CMCs simultaneously, stir into thick, slaking 45 minutes, making diameter with extruder is the 2mm strip particle, 100 ℃ of oven dry are 3 hours then.The oven dry rear catalyst is put into the muffle furnace roasting, and calcining heat is 460 ℃; Time is 10 hours.Promptly get catalyst.
Embodiment 2: solid acid is synthetic with embodiment 1.
Take by weighing 90 gram γ-Al respectively
2O
3, 1.5 the gram K
2MoO
4, 1 the gram KNO
3, 1.5 the gram solid acids, 4 the gram NaSiO
3(liquid) adds in the 500ml beaker that 80 gram deionized waters are housed, and adds 3 gram CMCs simultaneously, stir into thick, slaking 45 minutes, making diameter with extruder is the 2mm strip particle, 100 ℃ of oven dry are 3 hours then.The oven dry rear catalyst is put into the muffle furnace roasting, and calcining heat is 460 ℃; Time is 10 hours.Promptly get catalyst.
Embodiment 3: the solid acid synthetic method takes by weighing 88 gram γ-Al respectively with embodiment 1
2O
3, 1.5 the gram K
2MoO
4, 1 the gram KNO
3, 5 the gram solid acids, 4 the gram NaSiO
3(liquid) adds in the 500ml beaker that 80 gram deionized waters are housed, and adds 3 gram CMCs simultaneously, stir into thick, slaking 45 minutes, making diameter with extruder is the 2mm strip particle, 100 ℃ of oven dry are 3 hours then.The oven dry rear catalyst is put into the muffle furnace roasting, and calcining heat is 460 ℃; Time is 10 hours.Promptly get catalyst.
Embodiment 4: body acid synthetic method takes by weighing 90 gram γ-Al respectively with embodiment 1
2O
3, 2 the gram H
3PMo
12O
40, 1 the gram KNO
3, 5 the gram solid acids, 4 the gram NaSiO
3(liquid) adds in the 500ml beaker that 80 gram deionized waters are housed, and adds 3 gram CMCs simultaneously, stir into thick, slaking 45 minutes, making diameter with extruder is the 2mm strip particle, 100 ℃ of oven dry are 3 hours then.The oven dry rear catalyst is put into the muffle furnace roasting, and calcining heat is 460 ℃; Time is 10 hours.Promptly get catalyst.
The evaluating catalyst method:
With making the particle that catalyst is cut into long 1.5mm diameter 2mm, get 100ml, to put in the middle of the heating tube of the long 600mm of diameter 40mm, the heating tube two ends respectively add the porcelain ring of 200mm.Feed N
2Protection heats up 350 ℃, and 350 ℃ of temperature control heating add acetate (measuring pump is sent into), and ammonia is controlled by the flow agent.After the magnet ring preheating, enter the middle catalyst of heating tube.Gas is through cooling, product gas chromatographic analysis.
Table one evaluating catalyst result
Claims (9)
1. catalyst that is used for acetate and ammonia synthesis acetonitrile, it is characterized in that: each substance weight percentage composition is:
γ-Al
2O
385-90% K
2MoO
4Or H
3PMo
12O
401-5%
KNO
31-3% solid acid 3-8% NaSiO
32-6%.
2. a kind of catalyst that is used for acetate and ammonia synthesis acetonitrile according to claim 1 is characterized in that: containing Zr in the described solid acid, is benchmark with the weight of this catalyst, the weight percentage 2-6% of Zr.
3. make the described method that is used for the catalyst of acetate and ammonia synthesis acetonitrile of claim 1, it is characterized in that:
A, with γ-Al
2O
3, K
2MoO
4, KNO
3, solid acid and NaSiO
3Add in proportion in the agitator, add deionized water and a certain amount of CMC simultaneously, stir into thick;
B, with the mixture of viscous form slaking;
C, with the slaking mixture with extruder granulation and oven dry;
D, will dry catalyst muffle furnace roasting;
Catalyst cooling room temperature after e, the roasting promptly obtains catalyst of the present invention.
4. catalyst manufacture method according to claim 3 is characterized in that: described solid acid manufacture method is as follows: in proportion with ZrOCl
28H
2O and Al
2(SO
4)
38H
2O is dissolved in the deionized water, regulates pH value between 8-9 with ammoniacal liquor, must precipitate, and gained is precipitated ageing was filtered after 12 hours, drying, is the H of 1-10% with concentration
2SO
4Soaked 40 minutes, and after filtration, the drying, under 450 ℃ of conditions, obtained solid acid in 6 hours with the muffle furnace roasting.
5. catalyst manufacture method according to claim 4 is characterized in that: described ZrOCl
28H
2O and Al
2(SO
4)
38H
2The O mol ratio is 1: 1.
6. catalyst manufacture method according to claim 3 is characterized in that: the weight with this catalyst is benchmark, and the CMC weight percentage is 1.5% among the described step a.
7. catalyst manufacture method according to claim 3 is characterized in that: the curing time is 30-60 minute among the described step b.
8. catalyst manufacture method according to claim 3 is characterized in that: described step c extruding pelletization granularity is 2.5-5mm, bake out temperature 30-150 ℃, and 3 hours time.
9. catalyst manufacture method according to claim 3 is characterized in that: described steps d sintering temperature is 450-480 ℃, and the time is 10-20 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910066827A CN101856608A (en) | 2009-04-08 | 2009-04-08 | Catalyst for synthesizing acetonitrile by using acetic acid and ammonia and manufacturing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910066827A CN101856608A (en) | 2009-04-08 | 2009-04-08 | Catalyst for synthesizing acetonitrile by using acetic acid and ammonia and manufacturing method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101856608A true CN101856608A (en) | 2010-10-13 |
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|---|---|---|---|
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115582140A (en) * | 2022-11-29 | 2023-01-10 | 潍坊中汇化工有限公司 | Heteropolyacid catalyst for acetonitrile synthesis, preparation method and application |
-
2009
- 2009-04-08 CN CN200910066827A patent/CN101856608A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115582140A (en) * | 2022-11-29 | 2023-01-10 | 潍坊中汇化工有限公司 | Heteropolyacid catalyst for acetonitrile synthesis, preparation method and application |
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Application publication date: 20101013 |