CN107935886A - The preparation and its application of a kind of less toxic high-efficiency polymerization inhibitor of acrylonitrile installation - Google Patents
The preparation and its application of a kind of less toxic high-efficiency polymerization inhibitor of acrylonitrile installation Download PDFInfo
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- CN107935886A CN107935886A CN201711223739.9A CN201711223739A CN107935886A CN 107935886 A CN107935886 A CN 107935886A CN 201711223739 A CN201711223739 A CN 201711223739A CN 107935886 A CN107935886 A CN 107935886A
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- polymerization inhibitor
- component
- acrylonitrile
- less toxic
- acrylonitrile installation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/32—Separation; Purification; Stabilisation; Use of additives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
- C07C255/06—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms of an acyclic and unsaturated carbon skeleton
- C07C255/07—Mononitriles
- C07C255/08—Acrylonitrile; Methacrylonitrile
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
One kind is used for high-efficiency polymerization inhibitor in Acrylonitrile Production.The polymerization inhibitor using compound between different classes of cooperative effect, greatly improve can one-component inhibition efficiency, be melted into part by introducing peace and quiet scattered composition and metallic blunt, can effectively solve the relevant issues caused by dirty dirty deposition.Water-soluble high-efficient polymerization inhibitor using the present invention, radical polymerization and the scattered dirty thing formed can be effectively inhibited, dirty thing is evenly dispersed in logistics, so as to avoid dirty thing from being separated out in production device for acrylic nitrile, the production run cycle of device can be extended.
Description
Technical field
The application belongs to acrylonitrile process field, high more particularly to a kind of low toxicity in acrylonitrile installation refining system
Imitate the preparation method and applications of polymerization inhibitor.
Background technology
Acrylonitrile is a kind of chemical intermediate having many uses, and is the basic of synthetic fibers, synthetic rubber, synthetic plastic etc.
Raw material.Acrylonitrile is important among the product of Propylene Series, and worldwide, the yield of acrylonitrile is in propylene
Polypropylene is only less than in row product, occupy second.But in process of production, due to the causing of double bond on its structural formula
It is active to learn Nature comparison, it may occur that autohemagglutination, copolymerization, hydrolysis etc. chemically react.Product yield is caused to decline, while polymer deposits
In system, the obstruction of heat exchanger, tower tray and process pipe is caused.
At present, the most common polymerization inhibitor of acrylonitrile installation is hydroquinone (abbreviation HQ), is typically incorporated within drying tower, dehydrogenation cyanogen
Acid tower and finishing column.But it is slow for radical reaction termination speed since (1) hydroquinone belongs to retarder in itself, so raw
More polymer can be still produced during production, is the principal element for influencing acrylonitrile installation long-term operation.Said units and
Equipment, which blocks, can cause loss of material, device parking and safety and environmental protection problem, seriously affect and restrict the long week of acrylonitrile installation
Phase safe and stable operation.(2) hydroquinone is solid in itself, needs to configure using water at the scene, due to solubility original less than normal
Cause, setup time is partially long, in configuration process, also easily causes flying dust, influences worker's health.
The content of the invention
For shortcoming of the prior art, the present invention provides a kind of low toxicity in acrylonitrile installation refining system
High-efficiency polymerization inhibitor prepares and its application method.The polymerization inhibitor can substitute the hydroquinone used at present completely.This polymerization inhibitor phase
For hydroquinone, it all can quickly suppress the radical polymerization of acrylonitrile, the effective run time for extending acrylonitrile installation.
Product polymerization inhibitor of the present invention is liquid, and industry spot can be used directly, and without preparing, and the polymerization inhibitor toxicity is far below to benzene two
Phenol, belongs to the new polymerization inhibitor of low toxic and environment-friendly.
Invention main points：
One kind is used for acrylonitrile installation refining system low toxicity high-efficiency polymerization inhibitor, and the polymerization inhibitor contains component A, component B with
Component C, component A are 2,5- di-t-butylcatechols, 2,6-di-tert-butyl p-cresol, 2.6- di-t-butyl -4- methoxybenzenes
Phenol；B component is N, N- diphenyl-para-phenylene diamines, N, N- diethyl p-phenylenediamines, N, N- di-sec-butyl-p-phenyl enediamines；Component C is
Hydroquinone (HQ).Component A: component B: component C mass ratio is 5~25: 5~25: 5~20, remaining is solvent.A is preferably
2.6- di-t-butyl -4- metoxyphenols, component B are preferably N, and N- di-sec-butyl-p-phenyl enediamines, component C is hydroquinone
(HQ), A: B: C mass ratio is preferably in a proportion of as 20~25: 5~10: 10~20.
Present invention also offers such polymerization inhibitor in the application method of acrylonitrile installation refining system, and above-mentioned polymerization inhibitor is noted
Enter the charging of drying/dehydrogenation cyanic acid/finishing column either in reflux or tower, on-line continuous injection, on the basis of acrylonitrile yield,
The mass concentration of addition is 20~300ppm.Preferred concentration is 20~150ppm
The present invention is on the principle Research foundation that dirty thing is formed in acrylonitrile installation, by laboratory and pilot-plant
What test obtained., acrylonitrile installation are frequently accompanied by the generation of some polymerisations, wherein acrylonitrile certainly in normal production
The polymerization that poly- or other such as hydrogen cyanide, methacrylaldehyde, acrylic acid, acrylamide byproduct of reaction produce can cause occur in system
Scale problems.In addition, the corrosion by-products produced in system, catalyst are divided into, the improper use of defoamer and PH controls are unstable
Deng can the generation of acceleration system polymer and the deposition of dirty thing.These dirty things are mostly with flake or the shape of crystalline polymer
Formula occurs.The generation of dirty thing can shorten the cycle of operation of the equipment such as tower, reboiler and heat exchanger and reduce production efficiency.It is general next
Say, the acrylonitrile polymerization fouling most serious of drying tower, dehydrogenation cyanic acid tower and finishing column.The costly of these dirty things is cleared up, is had
When need device to stop, to production cause very big economic loss.
Applicating cooperation effect theory of the present invention, have selected the more components mixing for having function groups structure and different vapour pressures concurrently
The polymerization inhibitor of making laughs of system.It is demonstrated experimentally that the polymerization inhibitor has very high polymerization inhibition performance in acrylonitrile distillation process.This be because
For：It is liquid phase mass transport process in the distillation process of acrylonitrile, so polymerization inhibitor is distributed in monomers acrylonitrile by its vapour pressure
Among gas phase and liquid phase.The higher polymerization inhibitor of vapour pressure prevents the polymerization of gas-phase propene nitrile；The relatively low polymerization inhibitor of vapour pressure prevents liquid
Phase acrylonitrile polymerization.And there is cooperative effect between polymerization inhibitor composition under different vapour pressures, improve the inhibition effect of one-component
Rate.
The polymerization inhibitor of the present invention is liquid, can directly fill and be not required to dilute, condensation point is low, while the toxicity of the product is much low
In hydroquinone, belong to the efficient polymerization inhibitor of low toxicity.There is no any influence, environmental protection safe to use on product and downstream unit.Cause
This present invention can be that acrylonitrile installation brings significant economic benefit and social benefit.
Embodiment：
With reference to embodiment, to specific statement of the invention.
Embodiment 1 takes 1000g to remove the acrylonitrile of polymerization inhibitor, and total reflux operation (operation temperature is done in following device：
100 DEG C, the time：30 minutes), 100ppm polymerization inhibitors are added respectively, and the polymer content then measured in product is 3.22g.
Embodiment 2 takes 1000g to remove the acrylonitrile of polymerization inhibitor, and total reflux operation (operation temperature is done in following device：
100 DEG C, the time：30 minutes), 100ppm polymerization inhibitors are added respectively, and the polymer content then measured in product is 2.86g.
Embodiment 3 takes 1000g to remove the acrylonitrile of polymerization inhibitor, and total reflux operation (operation temperature is done in following device：
100 DEG C, the time：30 minutes), 100ppm polymerization inhibitors are added respectively, and the polymer content then measured in product is 2.14g.
Embodiment 4 takes 1000g to remove the acrylonitrile of polymerization inhibitor, and total reflux operation (operation temperature is done in following device：
100 DEG C, the time：30 minutes), 100ppm polymerization inhibitors are added respectively, and the polymer content then measured in product is 2.23g.
Embodiment 5 takes 1000g to remove the acrylonitrile of polymerization inhibitor, and total reflux operation (operation temperature is done in following device：
100 DEG C, the time：30 minutes), 100ppm polymerization inhibitors are added respectively, and the polymer content then measured in product is 1.98g.
Embodiment 6 takes 1000g to remove the acrylonitrile of polymerization inhibitor, and total reflux operation (operation temperature is done in following device：
100 DEG C, the time：30 minutes), 100ppm polymerization inhibitors are added respectively, and the polymer content then measured in product is 1.76g.
Embodiment 7 takes 1000g to remove the acrylonitrile of polymerization inhibitor, and total reflux operation (operation temperature is done in following device：
100 DEG C, the time：30 minutes), 100ppm polymerization inhibitors are added respectively, and the polymer content then measured in product is 2.37g.
Embodiment 8 takes 1000g to remove the acrylonitrile of polymerization inhibitor, and total reflux operation (operation temperature is done in following device：
100 DEG C, the time：30 minutes), 100ppm polymerization inhibitors are added respectively, and the polymer content then measured in product is 2.86g.
Embodiment 9 takes 1000g to remove the acrylonitrile of polymerization inhibitor, and total reflux operation (operation temperature is done in following device：
100 DEG C, the time：30 minutes), 100ppm polymerization inhibitors are added respectively, and the polymer content then measured in product is 2.12g.
Comparative example 1 takes 1000g to remove the acrylonitrile of polymerization inhibitor, and total reflux operation (operation temperature is done in following device：
100 DEG C, the time：30 minutes), 100ppm polymerization inhibitor this polymerization inhibitor M are added respectively, and the polymer content then measured in product is
1.76g。
Comparative example 2 takes 1000g to remove the acrylonitrile of polymerization inhibitor, and total reflux operation (operation temperature is done in following device：
100 DEG C, the time：30 minutes), 100ppm polymerization inhibitors foreign countries polymerization inhibitor A is added respectively, then measures the polymer content in product
For 1.89g.
Comparative example 3 takes 1000g to remove the acrylonitrile of polymerization inhibitor, and total reflux operation (operation temperature is done in following device：
100 DEG C, the time：30 minutes), 100ppm polymerization inhibitors foreign countries polymerization inhibitor B is added respectively, then measures the polymer content in product
For 2.11g.
Comparative example 4 takes 1000g to remove the acrylonitrile of polymerization inhibitor, and total reflux operation (operation temperature is done in following device：
100 DEG C, the time：30 minutes), 100ppm hydroquinone of polymerization retarder is added respectively, and the polymer content then measured in product is
3.12g。
| Comparative example | Polymerization inhibitor | Additive amount ppm | Polymer g |
| 1 | This patent product M | 100 | 1.76 |
| 2 | External polymerization inhibitor A | 100 | 1.89 |
| 3 | External polymerization inhibitor B | 100 | 2.11 |
| 4 | Hydroquinone | 100 | 3.12 |
By that can be seen to embodiment and external product comparative example, under comparable sodium, this patent product is better than to benzene two
Phenol and external imported product.
Influence of the polymerization inhibitor for polymer under various concentrations：
By testing influence of the polymerization inhibitor for polymer under various concentrations, it can be seen that when always, inhibition dosage exceedes
After 150ppm, polymer still has downward trend, but be not it is obvious that in view of acrylonitrile installation production run into
This, so optimal use concentration is 50~150ppm.
This patent product, which is can be seen that, from following table toxicity correction data belongs to low toxic and environment-friendly product.
Claims (7)
1. a kind of less toxic high-efficiency polymerization inhibitor applied in acrylonitrile installation product purification system, substitutes hydroquinone completely, it is wrapped
Include component A, component B, component C and solvent.Component A: component B: component C mass ratio is 5~25: 5~25: 5~20, remaining is molten
Agent.
2. the less toxic high-efficiency polymerization inhibitor of acrylonitrile installation according to claim 1, it is characterized in that：Component A is 2,5- di-t-butyls
Catechol, 2,6-di-tert-butyl p-cresol, 2.6- di-t-butyl -4- metoxyphenols；B component is N, and N- diphenyl is to benzene two
Amine, N, N- diethyl p-phenylenediamines, N, N- di-sec-butyl-p-phenyl enediamines；Component C is hydroquinone (HQ).
3. according to the acrylonitrile installation of claim 1 or 2 low toxicity high-efficiency polymerization inhibitor, it is characterized in that：Component A is preferably 2.6- bis-
The tert-butyl group -4- metoxyphenols, component B are preferably N, and N- di-sec-butyl-p-phenyl enediamines, component C is hydroquinone (HQ).
4. A: B: C mass ratio is preferably in a proportion of with less toxic high-efficiency polymerization inhibitor, component according to the acrylonitrile installation of claims 1 to 3
For 20~25: 5~10: 10~20.
5. the less toxic high-efficiency polymerization inhibitor of acrylonitrile installation according to claims 1 to 4, its solvent is C8-C10Aromatic hydrocarbons.
It is 6. according to the acrylonitrile installation of claim 1 to 5 with less toxic high-efficiency polymerization inhibitor, polymerization inhibitor is online directly or after dilution
It is continuously injected into acrylonitrile installation, on the basis of acrylonitrile yield, implantation concentration is 20~300ppm.
It is 7. according to the acrylonitrile installation of claim 1 to 6 with less toxic high-efficiency polymerization inhibitor, polymerization inhibitor is online directly or after dilution
It is continuously injected into acrylonitrile installation, on the basis of acrylonitrile yield, implantation concentration is preferably 50~150ppm.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711223739.9A CN107935886B (en) | 2017-11-29 | 2017-11-29 | Preparation and use method of polymerization inhibitor for acrylonitrile device |
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| CN201711223739.9A CN107935886B (en) | 2017-11-29 | 2017-11-29 | Preparation and use method of polymerization inhibitor for acrylonitrile device |
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| CN107935886A true CN107935886A (en) | 2018-04-20 |
| CN107935886B CN107935886B (en) | 2020-06-02 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1366081A (en) * | 1963-05-24 | 1964-07-10 | Rhone Poulenc Sa | Dicyano-2, 4 butene-1 |
| CN1054973A (en) * | 1990-03-17 | 1991-10-02 | 兰州化学工业公司研究院 | High-efficiency polymerization inhibitor for acrylonitrile refining |
| CN106145395A (en) * | 2016-07-13 | 2016-11-23 | 北京誉天利化工有限公司 | A kind of water soluble dispersing agent and application thereof |
| CN106565537A (en) * | 2016-10-14 | 2017-04-19 | 北京万智石油化工有限公司 | Water soluble dispersing scale inhibitor and application of water soluble dispersing scale inhibitor in acrylonitrile production device |
-
2017
- 2017-11-29 CN CN201711223739.9A patent/CN107935886B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1366081A (en) * | 1963-05-24 | 1964-07-10 | Rhone Poulenc Sa | Dicyano-2, 4 butene-1 |
| CN1054973A (en) * | 1990-03-17 | 1991-10-02 | 兰州化学工业公司研究院 | High-efficiency polymerization inhibitor for acrylonitrile refining |
| CN106145395A (en) * | 2016-07-13 | 2016-11-23 | 北京誉天利化工有限公司 | A kind of water soluble dispersing agent and application thereof |
| CN106565537A (en) * | 2016-10-14 | 2017-04-19 | 北京万智石油化工有限公司 | Water soluble dispersing scale inhibitor and application of water soluble dispersing scale inhibitor in acrylonitrile production device |
Non-Patent Citations (1)
| Title |
|---|
| 张自义 等: "丙烯腈阻聚剂的研究", 《合成橡胶工业》 * |
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