CN102452954A - Method for increasing yield of acetonitrile in acrylonitrile production - Google Patents
Method for increasing yield of acetonitrile in acrylonitrile production Download PDFInfo
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- CN102452954A CN102452954A CN201010513632XA CN201010513632A CN102452954A CN 102452954 A CN102452954 A CN 102452954A CN 201010513632X A CN201010513632X A CN 201010513632XA CN 201010513632 A CN201010513632 A CN 201010513632A CN 102452954 A CN102452954 A CN 102452954A
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- acetonitrile
- acrylonitrile
- hydrocarbon
- ethanol
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention relates to a method for increasing the yield of acetonitrile in acrylonitrile production, and mainly solves the problem of low yield of a main product acrylonitrile and the acetonitrile by mixed ammoxidation in the prior art. The method comprises the following steps of: contacting raw materials such as hydrocarbon selected from propylene and propane, ethanol, ammonia gas and air with an ammoxidation catalyst to ensure that the hydrocarbon, the ethanol, the ammonia gas and oxygen react on the catalyst at high temperature to generate the acrylonitrile and the acetonitrile, and recovering the acrylonitrile and the acetonitrile, wherein the concentration of the ethanol is 94 to 100 weight percent. Through the technical scheme, the problem is well solved, and the method can be used in the industrial production of the acrylonitrile and the acetonitrile by hydrocarbon and ethanol mixed ammoxidation.
Description
Technical field
The present invention relates to the method for raising the output acetonitrile in a kind of acrylonitrile process, in the production device for acrylic nitrile reactor drum, feed ethanol, do not influencing basically under the prerequisite of principal product acrylonitrile yield and final product quality, improve the output of by product acetonitrile.
Background technology
The hydrocarbon alcohol mixing ammonia oxidation that the present invention relates to a kind of novelty is the method for mixture of nitriles.Specifically, the present invention relates at ammoxidation of propylene is the method that improves by product acetonitrile productive rate in the vinyl cyanide process.
To acetonitrile market development situation, can rely on existing production device for acrylic nitrile raising the output acetonitrile, to improve device economic benefit and synthesized competitiveness, the technical scheme that can take is following:
The one, adjustment acrylonitrile installation process operation parameter is realized the suitably purpose of raising the output acetonitrile product.Full scale plant test run(s) result shows suitable reduction temperature of reaction, can effectively improve the acetonitrile yield, but vinyl cyanide and three cyanogen (vinyl cyanide, acetonitrile and prussic acid) yield all descends to some extent.The 2nd, carry out the part displacement with the catalyzer of higher acetonitrile yield, can effectively improve by-product acetonitrile output.The 3rd, add ethanol raw material, increase production acetonitrile greatly.In propylene ammonoxidizing fluid bed reactor drum, add a certain amount of ethanol, carry out oxidative ammonolysis jointly with propylene, ammonia, air, can be when keeping acrylonitrile yield constant basically; Significantly improve the acetonitrile yield; This flexible method property is big, and less investment, instant effect.
Having had some patents to introduce feeds in the fluidized-bed reactor methyl alcohol or ethanol to produce prussic acid or acetonitrile.In addition, these reference further disclose can methyl alcohol or ethanol be introduced in the fluidized-bed reactor and have produced vinyl cyanide simultaneously to increase sub product prussic acid or acetonitrile.
For example, US 3911089, US4485079 and US5288473 relate to through methyl alcohol being injected the fluidized-bed contain the ammoxidation catalyst that is fit to produce vinyl cyanide and make methanol ammonoxidation produce prussic acid.This is the method for raising the output prussic acid in acrylonitrile process, and acrylonitrile yield can be affected.
It is the method for mixture of nitriles, acetonitrile and prussic acid that CN1240674C has introduced the alcohol mixture ammonia oxidation, and this method adds alcohol mixture or thick alcohol is raw material, though can increase production acetonitrile or prussic acid; But because reaction raw materials is many or purity is not high, coarse ethanol concentration can reduce the principal product acrylonitrile yield less than 94%; Acrylonitrile yield is less than 79%; And ethanol is difficult to transform fully, gives subsequent technique and brings difficulty separating of acetonitrile, and the real economy benefit is also not obvious.
The place of method of raising the output acetonitrile is in the present invention's acrylonitrile process different from the past: the present invention provides the method for raising the output acetonitrile in a kind of new acrylonitrile process; Under suitable alcohol concn and temperature of reaction; Under the ammoxidation catalyst effect, regulate the output of increasing production acetonitrile with the charge ratio of hydrocarbon through regulating ethanol, invest little, instant effect; Handiness is big, acetonitrile output have a big increase and principal product acrylonitrile yield and quality product unaffected.
Summary of the invention
Technical problem to be solved by this invention be exist to mix in the prior art ammonia oxidation to the principal product acrylonitrile yield low with the low problem of acetonitrile yield, the method for raising the output acetonitrile in a kind of new acrylonitrile process is provided.This method has principal product acrylonitrile yield height, acetonitrile output amplification variable range big and principal product acrylonitrile yield and the impregnable advantage of quality product.
In order to solve the problems of the technologies described above; The technical scheme that the present invention adopts is following: the method for raising the output acetonitrile in a kind of acrylonitrile process is a raw material with hydrocarbon, ethanol, ammonia and the air that is selected from propylene and propane, and raw material is contacted under 400～460 ℃ with ammoxidation catalyst; Reaction generates vinyl cyanide and acetonitrile; Recover acrylonitrile and acetonitrile, wherein hydrocarbon: ethanol: ammonia: the mol ratio of air is 1: 0.01～0.5: 0.9～1.5: 8.5～11.0, and used alcoholic acid weight percent concentration is 94～100%; Used ammoxidation catalyst comprises following general formula
A
aB
bC
cD
dBi
eMo
12O
x
A is selected from least a among Li, Na, K, Rb and the Cs in the formula;
B is selected from least a among Ca, Mn, Fe, Co, Ni, Mg and the Ba;
C is selected from least a among Cr, W, P, Ge, Nb and the Ta;
D is selected from least a in the REE;
The span of a is 0.01～2.5;
The span of b is 1～15;
The span of c is 0.01～5;
The span of d is 0.01～3;
The span of e is 0.01～3;
X satisfies the required Sauerstoffatom sum of each element valence in the catalyzer;
Wherein support of the catalyst is selected from silicon-dioxide, aluminum oxide or its mixture, and its consumption is 30～70% by weight percentage.
In the technique scheme, the raw materials components mole ratio preferable range of ethanol and hydrocarbon is 0.01～0.4: 1; The raw materials components mole ratio preferable range of ammonia and hydrocarbon is 1.0～1.4: 1; The raw materials components mole ratio preferable range of air and hydrocarbon is 8.8～10.5: 1; The temperature of reaction preferable range is 410～450 ℃; Alcohol concn preferable range by weight percentage is 95～100%.
The method of manufacture of catalyzer of the present invention does not have particular requirement, can be undertaken by well-established law.At first the catalyzer each component is processed solution, be mixed and made into slurry with carrier again, the spray-dried microspheroidal that is shaped to, catalyzer is processed in last roasting.The preparation of slurry is preferably undertaken by the CN1005248C method.
The raw material of making catalyzer of the present invention is:
Molybdenum component in the catalyzer is with molybdenum oxide or ammonium molybdate.
The most handy its nitrate salt of all the other each components, oxalate, oxyhydroxide, oxide compound maybe can be decomposed into the salt of oxide compound.
Raw material available silicon colloidal sol, silicon gel or both mixtures as carrier silicon-dioxide.If use silicon sol, its quality will meet the requirement of CN1005248C.
It is 47～55% back spraying dryings that the prepared slurry heating is concentrated to solid content.Spray-dryer available pressure formula, two streamings or centrifugal turntable formula, but, can guarantee that the catalyzer of processing has good size-grade distribution with centrifugal better.
The roasting of catalyzer can be divided into two stages and carry out: each element decomposition of salts and high-temperature roasting in the catalyzer.The catabolic phase temperature is preferably 200～300 ℃, and the time is 0.5～2 hour.Maturing temperature is 500～800 ℃, is preferably 520～700 ℃; Roasting time is 20 minutes to 2 hours.Above-mentioned decomposition and roasting are carried out respectively in two stoving ovens, also can in a stove, be divided into two zones, also can in the continous way rotary roasting furnace, accomplish simultaneously and decompose and roasting.In catalyst decomposes and roasting process, to feed an amount of air,, and prevent that catalyzer is by overreduction with generation catalytic activity phase.Use the specification of increasing production the required propylene of acetonitrile or propane, ammonia and molecular oxygen in this inventive method manufacturing vinyl cyanide identical with other ammoxidation catalyst of use.Though the low molecule saturated hydrocarbon content in the raw material propylene to the reaction did not influence, considers that from economic point of view density of propylene is more preferably greater than 85% (mole).Ammonia can be used fertilizer grade liquefied ammonia.Reaction desired molecule oxygen can be used pure oxygen from technical standpoint, oxygen enrichment and air, but from economy and the most handy air of security consideration.
Getting into the ammonia of fluidized-bed reactor and the mol ratio of propylene is between 0.9～1.5, is preferably 1.0～1.4.The mol ratio of air and propylene is 8.5～11.0, is preferably 8.8～10.5.If owing to some operational reason must with higher air than the time, can increase to 12, reaction is not had great effect.But from security consideration, the excess of oxygen in the reactant gases can not preferably be not more than 4% greater than 7% (volume).
Increase production acetonitrile with the inventive method, available existing production technique need not done any key technological transformation.The eluting gas that is fluidized-bed reactor is removed unreacted ammonia through neutralizing tower, with water at low temperature whole organic products is absorbed again.Absorption liquid gets high-purity propylene nitrile product through extractive distillation after dehydrogenation cyanic acid and the processed.
From oxidative ammonolysis rule and vinyl cyanide principal product yield and final product quality consideration, suitable alcohol concn and ratio have been introduced in the inventive method, under suitable reaction temperature and ammoxidation catalyst effect; Make under the impregnable condition of acrylonitrile yield and final product quality, the ethanol oxidative ammonolysis generates acetonitrile, and ethanol can transform fully; Part ethanol can generate vinyl cyanide through transforming, so acrylonitrile yield can reach more than 79.5%, even up to 81%; The acetonitrile productive rate significantly rises; Can reach 6.0%, amplification surpasses 100%, has obtained better technical effect.
The examination of the activity of the inventive method is in internal diameter is 38 millimeters fluidized-bed reactor, to carry out.Loaded catalyst 550 grams, reaction pressure 0.084MPa, the propylene load (WWH) of catalyzer is 0.06 hour
-1
The definition of propylene conversion, vinyl cyanide selectivity and once through yield is following in the present invention:
Through embodiment the present invention is done further elaboration below.
Embodiment
[embodiment 1]
Dissolve with adding water 11 grams and heating the back 1.6 gram sodium hydroxide and 4.1 restrains Pottasium Hydroxide, obtain material (A); 850.0 gram ammonium molybdates are dissolved in 60～90 ℃ of hot water of 800 grams, get material (B); With 157.5 gram Bismuth trinitrates, 286.8 gram manganous nitrates, 594.5 gram nickelous nitrates, 330.4 gram iron nitrates mixing, add water 340 grams, as material (C), take by weighing 26.6 gram praseodymium nitrates and 24.8 gram chromium nitrates after the heating for dissolving, add water 15 grams, get material (D).
With material (A) and 2475 gram weight concentration is that 40% silicon sol mixes; Under agitation add material (B), (C) and (D) successively; After fully stirring, get slurry; According to well-established law the slurry of processing is carried out the framboid moulding in spray-dryer; Be 89 millimeters at internal diameter at last, length be in the rotary roasting furnace of 1700 millimeters (
89 * 1700 millimeters) in 600 ℃ of roastings 2.0 hours, process and consist of:
50％K
0.15Na
0.1Fe
2.0Ni
5.0Mn
2.0Cr
0.6Pr
0.4Bi
0.85Mo
12.0O
x+50％SiO
2。
[embodiment 2～6 and comparative example 1～4]
Adopt the catalyzer that has different compositions in the following table with embodiment 1 essentially identical method preparation, and under following reaction conditions, carry out the reaction that ammoxidation of propylene generates vinyl cyanide with prepared catalyzer, the result sees table 1.
The reaction conditions of the foregoing description and comparative example is:
Reaction pressure 0.084MPa
Loaded catalyst 550 grams
Catalyzer propylene load (WWH) 0.06 hour
-1
Claims (6)
1. the method for raising the output acetonitrile in the acrylonitrile process is a raw material with hydrocarbon, ethanol, ammonia and the air that is selected from propylene and propane, and raw material is contacted under 400～460 ℃ with ammoxidation catalyst; Reaction generates vinyl cyanide and acetonitrile; Recover acrylonitrile and acetonitrile, wherein hydrocarbon: ethanol: ammonia: the mol ratio of air is 1: 0.01～0.5: 0.9～1.5: 8.5～11.0, and used alcoholic acid weight percent concentration is 94～100%; Used ammoxidation catalyst comprises following general formula
A
aB
bC
cD
dBi
eMo
12O
x
A is selected from least a among Li, Na, K, Rb and the Cs in the formula;
B is selected from least a among Ca, Mn, Fe, Co, Ni, Mg and the Ba;
C is selected from least a among Cr, W, P, Ge, Nb and the Ta;
D is selected from least a in the REE;
The span of a is 0.01～2.5;
The span of b is 1～15;
The span of c is 0.01～5;
The span of d is 0.01～3;
The span of e is 0.01～3;
X satisfies the required Sauerstoffatom sum of each element valence in the catalyzer;
Wherein support of the catalyst is selected from silicon-dioxide, aluminum oxide or its mixture, and its consumption is 30～70% by weight percentage.
2. according to the method for raising the output acetonitrile in the said acrylonitrile process of claim 1, the raw materials components mole ratio that it is characterized in that ethanol and hydrocarbon is 0.01～0.4: 1.
3. according to the method for raising the output acetonitrile in the said acrylonitrile process of claim 1, the raw materials components mole ratio that it is characterized in that ammonia and hydrocarbon is 1.0～1.4: 1.
4. according to the method for raising the output acetonitrile in the said acrylonitrile process of claim 1, the raw materials components mole ratio that it is characterized in that air and hydrocarbon is 8.8～10.5: 1.
5. according to the method for raising the output acetonitrile in the said acrylonitrile process of claim 1, it is characterized in that temperature of reaction is 410～450 ℃.
6. according to the method for raising the output acetonitrile in the said acrylonitrile process of claim 1, it is characterized in that alcohol concn is 95～100% by weight percentage.
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| CN201010513632.XA CN102452954B (en) | 2010-10-21 | 2010-10-21 | Method for increasing yield of acetonitrile in acrylonitrile production |
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|---|---|---|---|
| CN201010513632.XA CN102452954B (en) | 2010-10-21 | 2010-10-21 | Method for increasing yield of acetonitrile in acrylonitrile production |
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| CN102452954A true CN102452954A (en) | 2012-05-16 |
| CN102452954B CN102452954B (en) | 2014-03-05 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110498749A (en) * | 2019-09-25 | 2019-11-26 | 中国天辰工程有限公司 | A method of improving propylene or propane ammoxidation by-product acetonitrile and hydrogen cyanide |
| CN114230487A (en) * | 2021-12-29 | 2022-03-25 | 中国天辰工程有限公司 | Heat energy coupling system and heat energy coupling method for acrylonitrile and acetonitrile production |
| CN114315639A (en) * | 2021-12-29 | 2022-04-12 | 中国天辰工程有限公司 | Heat utilization system and heat utilization method for co-production of acrylonitrile and acetonitrile |
| CN114426503A (en) * | 2020-10-13 | 2022-05-03 | 中国石油化工股份有限公司 | Process for the preparation of dinitrile compounds |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03246269A (en) * | 1990-02-21 | 1991-11-01 | Asahi Chem Ind Co Ltd | Method for increasing yield of acetonitrile |
| CN101147867A (en) * | 2006-09-20 | 2008-03-26 | 中国石油化工股份有限公司 | Fluidized bed catalyst for oxidation of propene ammonia |
-
2010
- 2010-10-21 CN CN201010513632.XA patent/CN102452954B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03246269A (en) * | 1990-02-21 | 1991-11-01 | Asahi Chem Ind Co Ltd | Method for increasing yield of acetonitrile |
| CN101147867A (en) * | 2006-09-20 | 2008-03-26 | 中国石油化工股份有限公司 | Fluidized bed catalyst for oxidation of propene ammonia |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110498749A (en) * | 2019-09-25 | 2019-11-26 | 中国天辰工程有限公司 | A method of improving propylene or propane ammoxidation by-product acetonitrile and hydrogen cyanide |
| CN114426503A (en) * | 2020-10-13 | 2022-05-03 | 中国石油化工股份有限公司 | Process for the preparation of dinitrile compounds |
| CN114230487A (en) * | 2021-12-29 | 2022-03-25 | 中国天辰工程有限公司 | Heat energy coupling system and heat energy coupling method for acrylonitrile and acetonitrile production |
| CN114315639A (en) * | 2021-12-29 | 2022-04-12 | 中国天辰工程有限公司 | Heat utilization system and heat utilization method for co-production of acrylonitrile and acetonitrile |
| CN114230487B (en) * | 2021-12-29 | 2024-01-23 | 中国天辰工程有限公司 | Production heat energy coupling system and method for acrylonitrile and acetonitrile |
| CN114315639B (en) * | 2021-12-29 | 2024-01-23 | 中国天辰工程有限公司 | Heat utilization system and heat utilization method for co-production of acrylonitrile and acetonitrile |
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| CN102452954B (en) | 2014-03-05 |
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