CN108003057A - A kind of continuous cracking production method of 2- methylene -4- cyanobutyraldehydes - Google Patents
A kind of continuous cracking production method of 2- methylene -4- cyanobutyraldehydes Download PDFInfo
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- CN108003057A CN108003057A CN201711234797.1A CN201711234797A CN108003057A CN 108003057 A CN108003057 A CN 108003057A CN 201711234797 A CN201711234797 A CN 201711234797A CN 108003057 A CN108003057 A CN 108003057A
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- Prior art keywords
- methylene
- cyanobutyraldehydes
- norbornene
- production method
- cracking
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/32—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen
- C07C1/321—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a non-metal atom
- C07C1/323—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a non-metal atom the hetero-atom being a nitrogen atom
Abstract
The invention discloses a kind of continuous cracking production method of 2 methylene, 4 cyanobutyraldehyde, include the following steps：By 2 cyanoethyl of raw material, 5 norbornene, 2 aldehyde after preheating, it is sent into thin film evaporator gasification process 60 180 seconds, 2 cyanoethyl, 5 norbornene, 2 aldehyde of gas phase passes through gas-liquid separator, enter cracker after removing unvaporized 2 cyanoethyl, 5 norbornene, 2 aldehyde, cracking 30 60 seconds is carried out between 200 360 DEG C；Gas after cracking condenses to obtain 2 methylene, 4 cyanobutyraldehyde, 60 DEG C of condensation temperature 25 DEG C by level-one；Cyclopentadiene is recycled into B-grade condensation, 50 15 DEG C of condensation temperature, and the cyclopentadiene content of recycling is more than 98%, can be directly used for the synthesis of 5 norbornene, 2 aldehyde；The by-product polymerizing thing of unvaporized 2 cyanoethyl, 5 norbornene, 2 aldehyde synthesis enters recycling can.
Description
Technical field
The present invention relates to chemical raw material production field, and in particular to a kind of continuous cracking of 2- methylene -4- cyanobutyraldehydes
Production method.
Background technology
2-vhloro-5-chloromethylpyridine is the important intermediate for producing imidacloprid, acetamiprid and thiacloprid etc., 2- methylene-
4- cyanobutyraldehydes are the 4th during cyclopentadiene route production 2-vhloro-5-chloromethylpyridine, it is by by 2- cyanogen second
Base -5- Norbornene-2-carboxaldehydes carry out Pintsch process reaction gained.
At present used quantitative 2- cyanoethyls -5- in the production technology of above-mentioned 2- methylene -4- cyanobutyraldehydes
In Norbornene-2-carboxaldehyde input reaction kettle, under high vacuum environment heating the mode that is cracked carries out, due to 2- cyanoethyls-
5- Norbornene-2-carboxaldehydes are a kind of heat-sensitive materials, it also has the problem of polymerization except cracking at high temperature, so cracking yield
Low, product purity is low.Due to cyclopentadiene low boiling point, in high vacuum environment, recycling cannot be condensed before vacuum pump, can only be true
Recycled after sky pump, generated heat by the compression of vacuum pump, form polymerization, so the cyclopentadiene content of recycling is low and containing big
The dicyclopentadiene of amount, great obstacle is caused to reusing.Due to once feeding intake in reaction kettle, cracking process is difficult to fixed
Amount control, in 140-170 DEG C of temperature range, 2- cyanoethyl -5- Norbornene-2-carboxaldehydes largely crack, 170~210 DEG C of area
Between only a small amount of material cracking, so the matching of the device of condensation recovery of the configuration and cyclopentadiene to vacuum system is difficult
To reach rationally efficiently, the low obtained heat-sensitive materials 2- methylene -4- cyanobutyraldehydes that crack of vacuum cannot be transferred out of body in time
System, partial material form polymerization, cause the waste of material, the mismatch of cyclopentadiene device of condensation recovery, causes ring again
Pentadiene is evaporate into air, causes environmental pollution.Its reaction is as follows：
The content of the invention
To solve the above problems, the present invention provides a kind of continuous cracking production method of 2- methylene -4- cyanobutyraldehydes.
To achieve the above object, the technical solution taken of the present invention is：
A kind of continuous cracking production method of 2- methylene -4- cyanobutyraldehydes, includes the following steps：By raw material 2- cyanogen second
Base -5- Norbornene-2-carboxaldehydes are sent into thin film evaporator gasification process 60-180 seconds after preheating, the 2- cyanoethyls -5- of gas phase
Norbornene-2-carboxaldehyde passes through gas-liquid separator, enters cracker after removing unvaporized 2- cyanoethyl -5- Norbornene-2-carboxaldehydes,
Carried out between 200-360 DEG C cracking 30-60 second, heated time is short, and material fluidity is good, can barrelling or be pumped into coke life
Produce workshop；Gas after cracking condenses to obtain 2- methylene -4- cyanobutyraldehydes by level-one, and 25 DEG C -60 DEG C of condensation temperature, obtains
2- methylene -4- cyanobutyraldehydes content be more than 95%；Cyclopentadiene is recycled into B-grade condensation, condensation temperature -- 50--
15 DEG C, the cyclopentadiene content of recycling is more than 98%, can be directly used for the synthesis of 5- Norbornene-2-carboxaldehydes；Unvaporized 2- cyanogen
The by-product polymerizing thing of ethyl -5- Norbornene-2-carboxaldehydes synthesis enters recycling can.
Preferably, cracking feed amount can be adjusted between 1L-150000L.
Preferably, system vacuum is between -0.065--0.080MPa, preferably -0.070--0.072MPa
Preferably, the condensation temperature of 2- methylene -4- cyanobutyraldehydes is at 35 DEG C -45 DEG C；Cyclopentadiene condensation temperature is -45
℃--25℃。
Preferably, the evaporator uses scrapper thin film evaporator, and evaporator area can exist according to production capacity design requirement
0.1m2-100m2Between adjust, meet the production capacity of 1kg/h-96000kg/h.
Preferably, the gasification temperature of 2- cyanoethyls -5- Norbornene-2-carboxaldehydes is at 170 DEG C -260 DEG C.
Preferably, vapor-phase thermal cracking device uses shell and tube, gas compression distributor is housed in tubulation, to reduce the delay of tube wall
Layer, its area can be according to production capacity design requirement in 5m2-4000m2Between adjust, meet the production capacity of 1kg/h-96000kg/h.
Preferably, vapor-phase thermal cracking temperature is 260 DEG C -300 DEG C.
Preferably, the gas compression distributor in the vapor-phase thermal cracking device is made of multistage, expand and compress at intervals of
10cm-30cm, is preferably 15cm-20cm, the compression section diameter of material compression expander is smaller 5mm-30mm than tubulation diameter, preferably
For 10mm；The expansion segment diameter of material compression expander is smaller 15mm-30mm than tubulation diameter, is preferably 20mm.
The invention has the advantages that：
2- cyanoethyl -5- Norbornene-2-carboxaldehydes the cleavage rate of the present invention is more than 99.8%, 2- methylene -4- cyanobutyraldehydes
Yield be more than 98%, 2- methylene -4- cyanobutyraldehydes content be more than 95%, the rate of recovery of the cyclopentadiene before vacuum pump is big
The cyclopentadiene content recycled before 95%, vacuum pump is more than 98%.
Brief description of the drawings
Fig. 1 is the reacting flow chart of the embodiment of the present invention.
Embodiment
In order to which objects and advantages of the present invention are more clearly understood, the present invention is carried out with reference to embodiments further
Describe in detail.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to limit this hair
It is bright.
Embodiment 1
50kg2- cyanoethyl -5- Norbornene-2-carboxaldehydes are preheated to 140 DEG C by preheater, into by 0.2m2Scraper plate
Thin film evaporator, gas-liquid separator, 40m2The continuous cracking system of vapor-phase thermal cracking device, two and condenser and vacuum system composition,
Vacuum maintains 620mmHg.The gaseous phase outlet temperature for controlling scrapper thin film evaporator is 165 DEG C -175 DEG C, and lower part residual night mouthful goes out
Mouth temperature is 215 DEG C -220 DEG C.2- cyanoethyl -5- Norbornene-2-carboxaldehydes charging rates are 0.28L/min, control vapor-phase thermal cracking
Device outlet temperature is 260 DEG C, gas condensation sampling, LC analyses, cyclopentadiene content 10.2%, 2- methylene -4- cyanobutyraldehydes
Content 86.3%, 2- cyanoethyl -5- Norbornene-2-carboxaldehydes content 0.0012%, other 3.499%.First-stage condenser controls out
Mouth temperature is 40 DEG C -45 DEG C, sampling, LC analyses, cyclopentadiene content 0.1%, 2- methylene -4- cyanobutyraldehyde contents
95.3%, 2- cyanoethyl -5- Norbornene-2-carboxaldehydes content 0.008%, other 4.592%.Secondary condenser controls outlet temperature
For -35 DEG C, sampling, GC analyses, cyclopentadiene content 98.6%.
Embodiment 2
With embodiment 1, vacuum is adjusted to 700mmHg.Vapor-phase thermal cracking device exports sampling result：Cyclopentadiene content
6.3%, 2- methylene -4- cyanobutyraldehydes content 90.1%, 2- cyanoethyl -5- Norbornene-2-carboxaldehydes content 0.0025%, other
3.5975%.First-stage condenser outlet sampling, LC analyses, cyclopentadiene content 0.006%, 2- methylene -4- cyanobutyraldehydes contain
96.6%, 2- cyanoethyl -5- Norbornene-2-carboxaldehydes content 0.0045% is measured, other 3.389%.Secondary condenser control outlet
Temperature is -35 DEG C, sampling, GC analyses, cyclopentadiene content 96.8%.
Embodiment 3
With embodiment 2, vacuum 700mmHg.Vapor-phase thermal cracking device outlet temperature is adjusted to 280 DEG C.Sampling result is：Ring
Pentadiene content 6.31%, 2- methylene -4- cyanobutyraldehydes content 91.2%, 2- cyanoethyl -5- Norbornene-2-carboxaldehyde contents
0.0024%, other 2.488%.First-stage condenser outlet sampling, LC analyses, cyclopentadiene content 0.0076%, 2- methylene-
4- cyanobutyraldehydes content 97.2%, 2- cyanoethyl -5- Norbornene-2-carboxaldehydes content 0.0056%, other 2.7868%.Two level is cold
It is -35 DEG C that condenser, which controls outlet temperature, sampling, GC analyses, cyclopentadiene content 97.12%.
Embodiment 4
5000kg2- cyanoethyl -5- Norbornene-2-carboxaldehydes are preheated to 140 DEG C by preheater, into by 20m2Scrape
Plate thin film evaporator, gas-liquid separator, 800m2The continuous cracking system of vapor-phase thermal cracking device, two and condenser and vacuum system composition
System, vacuum maintain 700mmHg.The gaseous phase outlet temperature for controlling scrapper thin film evaporator is 165 DEG C -175 DEG C, lower part residual night mouthful
Outlet temperature is 215 DEG C -220 DEG C.2- cyanoethyl -5- Norbornene-2-carboxaldehydes charging rates are 28.5L/min, and control gas phase is split
It is 280 DEG C to solve device outlet temperature, gas condensation sampling, LC analyses, cyclopentadiene content 5.3%, 2- methylene -4- cyanobutyraldehydes
Content 91.4%, 2- cyanoethyl -5- Norbornene-2-carboxaldehydes content 0.0018%, other 3.298%.First-stage condenser controls out
Mouth temperature is 40 DEG C -45 DEG C, sampling, LC analyses, cyclopentadiene content 0.0042%, 2- methylene -4- cyanobutyraldehyde contents
96.4%, 2- cyanoethyl -5- Norbornene-2-carboxaldehydes content 0.0027%, other 3.593%.Secondary condenser control outlet temperature
Spend for -35 DEG C, sample, GC analyses, cyclopentadiene content 97.7%.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, without departing from the principle of the present invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (9)
1. a kind of continuous cracking production method of 2- methylene -4- cyanobutyraldehydes, it is characterised in that include the following steps：By original
Expect that 2- cyanoethyl -5- Norbornene-2-carboxaldehydes after preheating, are sent into thin film evaporator gasification process 60-180 seconds, the 2- of gas phase
Cyanoethyl -5- Norbornene-2-carboxaldehydes pass through gas-liquid separator, and it is laggard to remove unvaporized 2- cyanoethyl -5- Norbornene-2-carboxaldehydes
Enter cracker, cracking 30-60 seconds is carried out between 200-360 DEG C；Gas after cracking by level-one condense to obtain 2- methylene-
4- cyanobutyraldehydes, 25 DEG C -60 DEG C of condensation temperature；Cyclopentadiene is recycled into B-grade condensation, condensation temperature -- and 50--15 DEG C,
The cyclopentadiene content of recycling is more than 98%, can be directly used for the synthesis of 5- Norbornene-2-carboxaldehydes；Unvaporized 2- cyanoethyls-
The by-product polymerizing thing of 5- Norbornene-2-carboxaldehydes synthesis enters recycling can.
A kind of 2. continuous cracking production method of 2- methylene -4- cyanobutyraldehydes as claimed in claim 1, it is characterised in that
Cracking feed amount can be adjusted between 1L-150000L.
A kind of 3. continuous cracking production method of 2- methylene -4- cyanobutyraldehydes as claimed in claim 1, it is characterised in that
System vacuum is between -0.065--0.080MPa.
A kind of 4. continuous cracking production method of 2- methylene -4- cyanobutyraldehydes as claimed in claim 1, it is characterised in that
The condensation temperature of 2- methylene -4- cyanobutyraldehydes is at 35 DEG C -45 DEG C；Cyclopentadiene condensation temperature is at -45 DEG C -- and 25 DEG C.
A kind of 5. continuous cracking production method of 2- methylene -4- cyanobutyraldehydes as claimed in claim 1, it is characterised in that
The evaporator uses scrapper thin film evaporator, and evaporator area can be according to production capacity design requirement in 0.1m2-100m2Between adjust
Section, meets the production capacity of 1kg/h-96000kg/h.
A kind of 6. continuous cracking production method of 2- methylene -4- cyanobutyraldehydes as claimed in claim 1, it is characterised in that
The gasification temperature of 2- cyanoethyl -5- Norbornene-2-carboxaldehydes is at 170 DEG C -260 DEG C.
A kind of 7. continuous cracking production method of 2- methylene -4- cyanobutyraldehydes as claimed in claim 1, it is characterised in that
Vapor-phase thermal cracking device uses shell and tube, its area can be according to production capacity design requirement in 5m2-4000m2Between adjust, meet 1kg/h-
The production capacity of 96000kg/h.
A kind of 8. continuous cracking production method of 2- methylene -4- cyanobutyraldehydes as claimed in claim 1, it is characterised in that
Vapor-phase thermal cracking temperature is 260 DEG C -300 DEG C.
A kind of 9. continuous cracking production method of 2- methylene -4- cyanobutyraldehydes as claimed in claim 1, it is characterised in that
Gas compression distributor in the vapor-phase thermal cracking device is made of multistage, is expanded and is compressed at intervals of 10cm-30cm；Material pressure
The compression section diameter of reducing and expansion prop is smaller 5mm-30mm than tubulation diameter；The expansion segment diameter of material compression expander is than tubulation diameter
Small 15mm-30mm.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110511161A (en) * | 2019-09-11 | 2019-11-29 | 连云港埃森化学有限公司 | A kind of method that continuous cracking prepares 2-vhloro-5-chloromethylpyridine intermediate alkene nitrile aldehyde |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007238807A (en) * | 2006-03-09 | 2007-09-20 | Okayama Univ | Norbornene derivative with two polar groups at end positions, metathesis ring-opened polymer and their preparation process |
| CN206355627U (en) * | 2016-12-30 | 2017-07-28 | 河北野田农用化学有限公司 | It is a kind of to be used for the vacuum condensing unit of the aldehyde lyase of 2 cyanoethyl, 5 ENB 2 |
| CN206396090U (en) * | 2016-12-30 | 2017-08-11 | 河北野田农用化学有限公司 | A kind of aldehyde continuous cracking device of 5 ENB of 2 cyanoethyl 2 |
-
2017
- 2017-11-30 CN CN201711234797.1A patent/CN108003057A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007238807A (en) * | 2006-03-09 | 2007-09-20 | Okayama Univ | Norbornene derivative with two polar groups at end positions, metathesis ring-opened polymer and their preparation process |
| CN206355627U (en) * | 2016-12-30 | 2017-07-28 | 河北野田农用化学有限公司 | It is a kind of to be used for the vacuum condensing unit of the aldehyde lyase of 2 cyanoethyl, 5 ENB 2 |
| CN206396090U (en) * | 2016-12-30 | 2017-08-11 | 河北野田农用化学有限公司 | A kind of aldehyde continuous cracking device of 5 ENB of 2 cyanoethyl 2 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110511161A (en) * | 2019-09-11 | 2019-11-29 | 连云港埃森化学有限公司 | A kind of method that continuous cracking prepares 2-vhloro-5-chloromethylpyridine intermediate alkene nitrile aldehyde |
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Application publication date: 20180508 |