CN102452954B - 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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- CN102452954B CN102452954B CN201010513632.XA CN201010513632A CN102452954B CN 102452954 B CN102452954 B CN 102452954B CN 201010513632 A CN201010513632 A CN 201010513632A CN 102452954 B CN102452954 B CN 102452954B
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- acetonitrile
- ethanol
- acrylonitrile
- propylene
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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
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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 a kind of method of increasing yield of acetonitrile in acrylonitrile production, in production device for acrylic nitrile reactor, pass into ethanol, substantially do not affecting under the prerequisite of principal product acrylonitrile yield and final product quality, improve the output of by product acetonitrile.
Background technology
The method that the hydrocarbon alcohol mixing ammonia oxidation that the present invention relates to a kind of novelty is mixture of nitriles.Specifically, the present invention relates at ammoxidation of propylene is in vinyl cyanide process, to improve the method for by product acetonitrile productive rate.
For acetonitrile market development situation, can rely on existing production device for acrylic nitrile increasing yield of acetonitrile, to improve device economic benefit and synthesized competitiveness, the technical scheme that can take is as follows:
The one, adjust acrylonitrile installation process operation parameter, realize the object of suitable increasing yield of acetonitrile product.Full scale plant test run(s) result shows suitably to reduce temperature of reaction, can effectively improve acetonitrile yield, but vinyl cyanide and three cyanogen (vinyl cyanide, acetonitrile and prussic acid) yield all declines to some extent.The 2nd, with the catalyzer of higher acetonitrile yield, carry out part displacement, can effectively improve by-product acetonitrile output.The 3rd, add ethanol raw material, greatly increasing yield of acetonitrile.In propylene ammonoxidizing fluid bed reactor, add a certain amount of ethanol, jointly carry out oxidative ammonolysis with propylene, ammonia, air, can be when keeping acrylonitrile yield substantially constant, significantly improve acetonitrile yield, the method handiness is large, and less investment, instant effect.
Having had some patent Introductions passes in fluidized-bed reactor methyl alcohol or ethanol to produce prussic acid or acetonitrile.In addition, these reference further disclose and can will in methyl alcohol or ethanol introducing fluidized-bed reactor, to increase byproduct prussic acid or acetonitrile, produce vinyl cyanide simultaneously.
For example, the fluidized-bed that US 3911089, US4485079 and US5288473 relate to by methyl alcohol injection is contained to the ammoxidation catalyst that is applicable to production vinyl cyanide makes methanol ammonoxidation produce prussic acid.This is the method for increasing production 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 alcohol mixture ammonia oxidation, this method adds alcohol mixture or thick alcohol is raw material, although energy increasing yield of acetonitrile or prussic acid, but because reaction raw materials is many or purity is not high, coarse ethanol concentration is less than 94%, can reduce principal product acrylonitrile yield, acrylonitrile yield is less than 79%, and ethanol is difficult to transform completely, give separated the bring difficulty of subsequent technique with acetonitrile, real economy benefit is also not obvious.
The place of the method for the present invention's increasing yield of acetonitrile in acrylonitrile production different from the past is: a kind of method that the invention provides new increasing yield of acetonitrile in acrylonitrile production, under suitable alcohol concn and temperature of reaction, under ammoxidation catalyst effect, by the charge ratio of adjusting ethanol and hydrocarbon, regulate the output of increasing yield of acetonitrile, invest little, instant effect, handiness is large, 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 in prior art, exist to mix ammonia oxidation to principal product acrylonitrile yield the low and low problem of acetonitrile yield, a kind of method of new increasing yield of acetonitrile in acrylonitrile production is provided.It is high that the method has principal product acrylonitrile yield, acetonitrile output amplification variable range large 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 solution used in the present invention is as follows: a kind of method of increasing yield of acetonitrile in acrylonitrile production, hydrocarbon, ethanol, ammonia and the air that is selected from propylene and propane of take is raw material, raw material is contacted at 400～460 ℃ with ammoxidation catalyst, reaction generates vinyl cyanide and acetonitrile, recover acrylonitrile and acetonitrile, hydrocarbon wherein: ethanol: ammonia: the mol ratio of air is 1: 0.01～0.5: 0.9～1.5: 8.5～11.0, the weight percent concentration of ethanol used is 94～100%, ammoxidation catalyst used comprises following general formula
A
aB
bC
cD
dBi
eMo
12O
x
In formula, A is selected from least one in Li, Na, K, Rb and Cs;
B is selected from least one in Ca, Mn, Fe, Co, Ni, Mg and Ba;
C is selected from least one in Cr, W, P, Ge, Nb and Ta;
D is selected from least one in rare earth element;
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 meets the required Sauerstoffatom sum of each element valence in 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 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; Temperature of reaction preferable range is 410～450 ℃; Alcohol concn by weight percentage preferable range is 95～100%.
The manufacture method of catalyzer of the present invention there is no particular requirement, can be undertaken by well-established law.First catalyzer each component is made to solution, then be mixed and made into slurry with carrier, the spray-dried microspheroidal that is shaped to, catalyzer is made in last roasting.The preparation of slurry is preferably undertaken by CN1005248C method.
The raw material of manufacturing catalyzer of the present invention is:
Molybdenum oxide or ammonium molybdate for molybdenum component in catalyzer.
The most handy its nitrate of all the other each components, oxalate, oxyhydroxide, oxide compound maybe can be decomposed into the salt of oxide compound.
Raw material as carrier silicon-dioxide can be used silicon sol, silicon gel or both mixtures.If with silicon sol, its quality will meet the requirement of CN1005248C.
It is that 47～55% rear sprayings are dry that the slurry heating preparing is concentrated to solid content.Spray-dryer available pressure formula, two streamings or centrifugal turntable formula, but with centrifugal better, can guarantee that the catalyzer of making has good size-grade distribution.
The roasting of catalyzer can be divided into two stages and carry out: the decomposition of each element salt and high-temperature roasting in catalyzer.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 regions, also can in continous way rotary roasting furnace, complete simultaneously and decompose and roasting.In catalyst decomposes and roasting process, to pass into appropriate air, to generate Catalytic active phase, and prevent that catalyzer is by over reduction.Use this inventive method to manufacture the specification of the required propylene of increasing yield of acetonitrile in vinyl cyanide or propane, ammonia and molecular oxygen identical with other ammoxidation catalyst of use.Although the low molecule saturated hydrocarbon content in raw material propylene there is no impact to reaction, from economic point of view consider density of propylene 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.
Entering 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 due to some operational reason must with higher air than time, can increase to 12, reaction is not had to a great effect.But from security consideration, the excess of oxygen in reactant gases can not be greater than 7% (volume), is preferably not more than 4%.
Use the inventive method increasing yield of acetonitrile, available existing production technique, does not need to do any key technological transformation.The eluting gas that is fluidized-bed reactor is removed unreacted ammonia through neutralizing tower, then by water at low temperature, whole organic products is absorbed.Absorption liquid, through extractive distillation, obtains high-purity propylene nitrile product after dehydrogenation cyanic acid and processed.
From oxidative ammonolysis rule and vinyl cyanide principal product yield and final product quality consideration, suitable alcohol concn and ratio in the inventive method, have been introduced, under suitable temperature of reaction and ammoxidation catalyst effect, make under the impregnable condition of acrylonitrile yield and final product quality, ethanol oxidative ammonolysis generates acetonitrile, and ethanol can transform completely, part ethanol can generate vinyl cyanide through transforming, therefore acrylonitrile yield can reach more than 79.5%, even, up to 81%, acetonitrile productive rate significantly rises, and can reach 6.0%, amplification surpasses 100%, has obtained good technique effect.
The activity examination of the inventive method is to carry out in internal diameter is the fluidized-bed reactor of 38 millimeters.550 grams of loaded catalysts, reaction pressure 0.084MPa, the propylene load (WWH) of catalyzer is 0.06 hour
-1.
Propylene conversion, vinyl cyanide selectivity and once through yield are defined as follows in the present invention:
Below by embodiment, the present invention is further elaborated.
Embodiment
[embodiment 1]
1.6 grams of sodium hydroxide and 4.1 grams of potassium hydroxide dissolve with adding after 11 grams, water also heats, and obtain material (A); 850.0 grams of ammonium molybdates are dissolved in 800 grams of 60～90 ℃ of hot water, obtain material (B); 157.5 grams of Bismuth trinitrates, 286.8 grams of manganous nitrates, 594.5 grams of nickelous nitrates, 330.4 grams of iron nitrates are mixed, add 340 grams, water, after heating for dissolving, as material (C), take 26.6 grams of praseodymium nitrates and 24.8 grams of chromium nitrates, add 15 grams, water, obtain material (D).
The silicon sol that is 40% with 2475 gram weight concentration by material (A) mixes, under agitation add successively material (B), (C) and (D), after fully stirring, obtain slurry, according to well-established law, the slurry of making is carried out in spray-dryer to framboid moulding, at internal diameter, be finally 89 millimeters, length be 1700 millimeters (
89 * 1700 millimeters) rotary roasting furnace in 600 ℃ of roastings 2.0 hours, make 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 method preparation substantially the same manner as Example 1 to there are the different catalyzer that form in following table, and with prepared catalyzer, under following reaction conditions, carry out the reaction that ammoxidation of propylene generates vinyl cyanide, the results are shown in Table 1.
The reaction conditions of above-described embodiment and comparative example is:
Reaction pressure 0.084MPa
550 grams of loaded catalysts
Catalyzer propylene load (WWH) 0.06 hour
-1
Claims (1)
1. a method for increasing yield of acetonitrile in acrylonitrile production, hydrocarbon, ethanol, ammonia and the air that is selected from propylene and propane of take is raw material, and raw material is contacted with ammoxidation catalyst, reaction generates vinyl cyanide and acetonitrile; Concrete steps are:
1.6 grams of sodium hydroxide and 4.1 grams of potassium hydroxide dissolve with adding after 11 grams, water also heats, and obtain material A; 850.0 grams of ammonium molybdates are dissolved in 800 grams of 60～90 ℃ of hot water, obtain material B; 157.5 grams of Bismuth trinitrates, 286.8 grams of manganous nitrates, 594.5 grams of nickelous nitrates, 330.4 grams of iron nitrates are mixed, add 340 grams, water, after heating for dissolving, as material C, take 26.6 grams of praseodymium nitrates and 24.8 grams of chromium nitrates, add 15 grams, water, obtain material D;
The silicon sol that is 40% with 2475 gram weight concentration by material A mixes, under agitation add successively material B, C and D, after fully stirring, obtain slurry, according to well-established law, the slurry of making is carried out in spray-dryer to framboid moulding, at internal diameter, it is finally 89 millimeters, length be in the rotary roasting furnace of 1700 millimeters in 600 ℃ of roastings 2.0 hours, make 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; X meets the required Sauerstoffatom sum of each element valence in catalyzer;
Reaction exists
in millimeter fluidized-bed reactor, carry out; Reaction pressure is 0.084MPa; Loaded catalyst is 550 grams; Catalyzer propylene load, is also WWH, is 0.06 hour
-1;
The concentration of ethanol is 99wt%, and the volume ratio of ethanol and propylene is 0.05, and the volume ratio of ammonia and propylene is 1.3, and the volume ratio of air and propylene is 9.8; Temperature of reaction is 430 ℃; The result of reaction is: acrylonitrile yield is 80.9%, and acetonitrile yield is 3.8%.
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| 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 |
| CN114426503B (en) * | 2020-10-13 | 2024-07-09 | 中国石油化工股份有限公司 | Process for producing dinitrile compound |
| 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 |
| 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 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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| JPH03246269A (en) * | 1990-02-21 | 1991-11-01 | Asahi Chem Ind Co Ltd | Method for increasing yield of acetonitrile |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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| JP平3-246269A 1991.11.01 |
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