CN106905188A - A kind of polymerization inhibitor and its application in production device for acrylic nitrile - Google Patents
A kind of polymerization inhibitor and its application in production device for acrylic nitrile Download PDFInfo
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- CN106905188A CN106905188A CN201710102874.1A CN201710102874A CN106905188A CN 106905188 A CN106905188 A CN 106905188A CN 201710102874 A CN201710102874 A CN 201710102874A CN 106905188 A CN106905188 A CN 106905188A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/24—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons
- C07C253/26—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons containing carbon-to-carbon multiple bonds, e.g. unsaturated aldehydes
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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
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/32—Separation; Purification; Stabilisation; Use of additives
- C07C253/34—Separation; Purification
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A kind of application the invention discloses polymerization inhibitor and its in production device for acrylic nitrile.The polymerization inhibitor includes：Component A, component B and component C, component A are the alkyl N heterocyclic compounds containing NO free radical, and component B is butylated hydroxy anisole, and component C is p-tert-Butylcatechol, wherein component A：Component B：The mass ratio of component C is 6 20：1‑5：10‑30.Using polymerization inhibitor of the invention, can effectively suppress the radical polymerization of acrylonitrile, significantly the production run cycle of extension fixture.
Description
Technical field
The invention belongs to acrylonitrile process technical field, more particularly to one kind is applied and dried in production device for acrylic nitrile
The preparation method and applications of the polymerization inhibitor of tower, dehydrogenation cyanic acid tower or finishing column.
Background technology
Acrylonitrile (AN) is the important monomer in organic synthesis industry.Because the double bond on its structural formula causes chemical property
Compare active, it may occur that autohemagglutination, copolymerization, hydrolysis etc. chemically react.In process of manufacture
In, due to the generation of acrylonitrile polymerization, on the one hand, cause product yield to decline；On the other hand, polymer deposits are in system
It is interior, cause the obstruction of heat exchanger, tower tray and process pipe.
At present, the most frequently used polymerization inhibitor of acrylonitrile installation is hydroquinones（Abbreviation HQ）, generally it is added into drying tower, takes off
In hydrogen cyanide tower and finishing column.But because the polymerization inhibition effect of hydroquinones is poor, so above-mentioned position still can in process of production
More polymer is produced, is the principal element for influenceing acrylonitrile installation long-term operation.Said units and equipment are blocked and can made
Into loss of material, device stops and safety and environmental protection problem, has a strong impact on and restrict the long period safety and stability fortune of acrylonitrile installation
OK.
The content of the invention
For weak point of the prior art, the invention provides a kind of polymerization inhibitor and its in production device for acrylic nitrile
Application.Using polymerization inhibitor of the invention, can effectively suppress the radical polymerization of acrylonitrile, significantly the production of extension fixture
The cycle of operation.
Polymerization inhibitor of the invention, including：Component A, component B and component C, component A are that the alkyl-N- containing NO free radical is miscellaneous
Cycle compound, component B is butylated hydroxy anisole, and component C is p-tert-Butylcatechol, wherein component A：Component B：Component C
Mass ratio be 6-20：1-5：10-30, preferably 8 ~ 18：2-5：12-25.
In polymerization inhibitor of the invention, the structure of the compound of alkyl-N-heterocycle containing NO free radical is as follows：
Wherein R1, R2, R3, R4 and R5 can be hydrogen, hydroxyl, alkyl, aryl, alkylaryl or aryl alkyl, R1, R2, R3, R4
Can be with identical with R5, it is also possible to different, carbon number is 0-10, and R1, R2, R3, R4 it is different with the carbon number of R5 when be
0。
Being preferably R1, R2, R4 and R5 in polymerization inhibitor of the invention, in the compound of alkyl-N-heterocycle containing NO free radical is
Methyl, R3 is hydroxyl, i.e. 4- hydroxyl -2,2,6,6- tetramethyl piperidine -1- oxygen radicals.
Present invention also offers application of the above-mentioned polymerization inhibitor in production device for acrylic nitrile, especially filled in acrylonitrile process
Application in drying tower, dehydrogenation cyanic acid tower and/or the finishing column put, it is specific as follows：Above-mentioned polymerization inhibitor is injected into drying tower, is taken off
In hydrogen cyanide tower and/or finishing column, can mix with charging and/or reflux in injection tower, it is also possible to be separately injected into tower, it is excellent
It is selected in line to be continuously injected into, the mass concentration of polymerization inhibitor is 10 ~ 200ppm, preferably 40 ~ 150ppm.
The present invention is obtained on the principle Research foundation of dirty thing formation in production device for acrylic nitrile.Acrylonitrile process
Device is main to be made up of operations such as reaction, chilling, absorption, recovery, refined, four-effect evaporations, and acrylonitrile installation is in normal production
Be frequently accompanied by the generation of some polymerisations, wherein acrylonitrile autohemagglutination or other such as hydrogen cyanide, methacrylaldehyde, acrylic acid, propylene
The polymerization that the byproducts of reaction such as acid amides are produced can cause occur scale problems in system.In addition, the corrosion by-product produced in system
Thing, catalyst are decomposed, the improper use of defoamer and pH control shakinesses etc., can acceleration system polymer generation and dirty thing
Deposition.These dirty things occur in the form of flake or crystalline polymer mostly.The generation of dirty thing can shorten tower, reboiler and change
The cycle of operation of the equipment such as hot device and reduction production efficiency.In general, the acrylonitrile of drying tower, dehydrogenation cyanic acid tower and finishing column
Polymerization fouling is more serious.Clear up the costly of these dirty things, it is sometimes desirable to which device stops, very big economic damage is caused to production
Lose.
It is generally believed that the mechanism that production device for acrylic nitrile dirt thing is produced is as follows：
The activity of acrylonitrile is at a relatively high, and spontaneous polymerization is easily produced under the situation in heating and containing iron powder, and this polymerization is anti-
Should be to be completed via the approach of radical chain reaction.Radical chain reaction includes three steps successively：Chain initiation reaction, chain increase
Reaction and chain termination reaction.In chain initiating stage, temperature higher or contacting metal（Such as equipment surface or corrosion by-products）
Generation free radical can be catalyzed, these free radicals are referred to as chain initiator, polymerisation process can be accelerated by two ways, depended on
Whether there is oxygen or peroxide in medium.
If there is oxygen or peroxide, chain initiator rapidly will generate peroxylradicals with oxygen reaction；Peroxide
Changing free radical will be further with monomer reaction so that produces more free radicals.The chain growth that this oxygen is participated in is commonly known as
Auto-oxidation reaction.
In the absence of oxygen, chain reaction initiator and monomer reaction generate new free radical, and the process can be carried out constantly,
Combined with more monomers, until chain reaction is terminated.Chain termination reaction is generally given birth to by the reaction and living radical between
Reached into the molecule without activity.
Polymerization inhibitor of the present invention can be used alone, it is also possible to be applied in combination with other anti-fouling agents, and described other anti-fouling agents can
Think one or more in dispersant, polymerization inhibitor, corrosion inhibitor, defoamer etc..Low toxicity of the invention is efficiently inhibited
Agent can Quick stop Raolical polymerizable, and remove the trace oxygen in system, terminate the generation of polymer.
Polymerization inhibitor of the invention is liquid, can directly fill and be not required to dilution, and condensation point is low, while the toxicity of the product is much low
In hydroquinones, also below the similar polymerization inhibitor product for replacing hydroquinones both at home and abroad, belong to the efficient polymerization inhibitor of low toxicity.To producing
Product and downstream unit use safety and environmental protection without not influenceing substantially.Therefore the present invention can bring for production device for acrylic nitrile
Significant economic benefit and social benefit.
Specific embodiment
Polymerization inhibitor of the invention is described in detail with reference to embodiment, but protection scope of the present invention not office
It is limited to embodiment.
The composition and proportioning of the polymerization inhibitor used by comparative example 1-3 and embodiment of the present invention 1-4 are shown in Tables 1 and 2 respectively.
Comparative example 7 is the application result for being added without polymerization inhibitor.Comparative example 8,9 and 10 is respectively using hydroquinones, external product A（Board
Number be EC3457A）With external product B（The trade mark is DA7641）Application result.Embodiment 5-8 is respectively embodiment of the present invention 1-
The application result of 4 polymerization inhibitors, comparative example 4-6 is respectively the application result of comparative example 1-3 polymerization inhibitors, is shown in Table 3.Embodiment 9-13 is
Using application result of the polymerization inhibitor of embodiment 2 under different concentrations, 4 are shown in Table.
The comparative example 1-3 of table 1 and embodiment 1-4 polymerization inhibitors are constituted
| It is raw materials used | Component A | Component B | Component C |
| Comparative example 1 | 4- hydroxyl -2,2,6,6- tetramethyl piperidine -1- oxygen radicals | - | - |
| Comparative example 2 | - | Butylated hydroxy anisole | - |
| Comparative example 3 | - | - | P-tert-Butylcatechol |
| Embodiment 1 | 4- hydroxyl -2,2,6,6- tetramethyl piperidine -1- oxygen radicals | Butylated hydroxy anisole | P-tert-Butylcatechol |
| Embodiment 2 | 4- hydroxyl -2,2,6,6- tetramethyl piperidine -1- oxygen radicals | Butylated hydroxy anisole | P-tert-Butylcatechol |
| Embodiment 3 | 4- hydroxyl -2,2,6,6- tetramethyl piperidine -1- oxygen radicals | Butylated hydroxy anisole | P-tert-Butylcatechol |
| Embodiment 4 | 4- hydroxyl -2,2,6,6- tetramethyl piperidine -1- oxygen radicals | Butylated hydroxy anisole | P-tert-Butylcatechol |
The proportioning of the comparative example 1-3 of table 2 and embodiment 1-4 polymerization inhibitors
（Data are mass fraction in table）
| It is raw materials used | Component A | Component B | Component C |
| Comparative example 1 | 10 | - | - |
| Comparative example 2 | - | 5 | - |
| Comparative example 3 | - | - | 15 |
| Embodiment 1 | 15 | 3 | 15 |
| Embodiment 2 | 15 | 4 | 20 |
| Embodiment 3 | 12 | 5 | 22 |
| Embodiment 4 | 10 | 5 | 15 |
Take in appropriate polymerization inhibitor addition acrylonitrile, total reflux operation is carried out under the following conditions（Operation temperature：100 DEG C, time：
30 minutes）, then blank testing and add polymer content in different polymerization inhibitor products.
The application result of the comparative example of table 3 and embodiment polymerization inhibitor
| Polymerization inhibitor | Polymerization inhibitor consumption, ppm | Polymer content, g/1500mL AA | |
| Comparative example 7 | - | - | 21.2 |
| Comparative example 8 | Hydroquinones | 100 | 6.85 |
| Comparative example 9 | External product A | 100 | 3.12 |
| Comparative example 10 | External product B | 100 | 3.2 |
| Embodiment 5 | Embodiment 1 | 100 | 2.14 |
| Embodiment 6 | Embodiment 2 | 100 | 1.95 |
| Embodiment 7 | Embodiment 3 | 100 | 2.15 |
| Embodiment 8 | Embodiment 4 | 100 | 2.33 |
| Comparative example 4 | Comparative example 1 | 100 | 4.92 |
| Comparative example 5 | Comparative example 2 | 100 | 4.77 |
| Comparative example 6 | Comparative example 3 | 100 | 5.93 |
From table 3 it can be seen that product of the present invention is under comparable sodium, the polymerization inhibition effect to acrylonitrile is far longer than hydroquinones,
Also it is significantly better than external similar acrylonitrile inhibition product.
The embodiment 9-13 of table 4 is the application result using the polymerization inhibitor of embodiment 2 under different concentrations
| Inhibitor concentration, ppm | 0 | 20 | 40 | 100 | 150 | 200 |
| Flask interpolymer content, g/1500mL AA | 21.2 | 3.68 | 2.92 | 1.95 | 1.13 | 0.85 |
From table 4, it can be seen that raising of the product of the present invention with implantation concentration, polymerization inhibition effect also accordingly strengthens, but is being more than
After 150ppm, the increased amplitude of polymerization inhibition effect start reduce, so cost-effective implantation concentration be 40-150ppm it
Between.
Product of the present invention is can be seen that from the toxicity correction data of table 5 belong to low toxic and environment-friendly product.
The toxicity correction data of table 5
| Hydroquinones | External product A | External product B | The polymerization inhibitor of embodiment 2 | |
| Toxicity data LD50 Oral Administration in Rats, mg/kg | 320 | ≥500 | ≥500 | ≥4000 |
Claims (8)
1. a kind of polymerization inhibitor, including：Component A, component B and component C, component A are the alkyl-N-heterocycle chemical combination containing NO free radical
Thing, component B is butylated hydroxy anisole, and component C is p-tert-Butylcatechol, wherein component A：Component B：The quality of component C
Than being 6-20：1-5：10-30.
2. according to the polymerization inhibitor described in claim 1, it is characterised in that：Component A：Component B：The mass ratio of component C is 8 ~ 18：2-
5：12-25.
3. according to the polymerization inhibitor described in claim 1, it is characterised in that：The knot of the compound of alkyl-N-heterocycle containing NO free radical
Structure is as follows：
,
Wherein R1, R2, R3, R4 and R5 are hydrogen, hydroxyl, alkyl, aryl, alkylaryl or aryl alkyl, R1, R2, R3, R4 and R5
Identical or different, carbon number is 0-10, and R1, R2, R3, R4 it is different with the carbon number of R5 when be 0.
4. according to the polymerization inhibitor described in claim 1, it is characterised in that the compound of alkyl-N-heterocycle containing NO free radical is 4- hydroxyls
Base -2,2,6,6- tetramethyl piperidine -1- oxygen radicals.
5. application of a kind of polymerization inhibitor in production device for acrylic nitrile, including by any described polymerization inhibitor of claim 1 ~ 4 its
Add in the liquid phase of production device for acrylic nitrile, addition mass concentration is 10 ~ 200ppm, preferably 40 ~ 150ppm.
6. according to the application described in claim 5, it is characterised in that：By the polymerization inhibitor inject drying tower, dehydrogenation cyanic acid tower and/
Or in finishing column, or mix in injection tower with charging and/or reflux, or be separately injected into tower.
7. according to the application described in claim 5 or 6, it is characterised in that：The polymerization inhibitor on-line continuous injection.
8. according to the application described in claim 5, it is characterised in that：The polymerization inhibitor is used alone, or with other anti-fouling agents
It is applied in combination, described other anti-fouling agents are one or more in dispersant, polymerization inhibitor, corrosion inhibitor, defoamer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710102874.1A CN106905188A (en) | 2017-02-24 | 2017-02-24 | A kind of polymerization inhibitor and its application in production device for acrylic nitrile |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710102874.1A CN106905188A (en) | 2017-02-24 | 2017-02-24 | A kind of polymerization inhibitor and its application in production device for acrylic nitrile |
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| CN106905188A true CN106905188A (en) | 2017-06-30 |
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| CN201710102874.1A Pending CN106905188A (en) | 2017-02-24 | 2017-02-24 | A kind of polymerization inhibitor and its application in production device for acrylic nitrile |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109575924A (en) * | 2017-09-29 | 2019-04-05 | 中国石油天然气股份有限公司 | Compound polymerization inhibitor and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1259114A (en) * | 1997-06-13 | 2000-07-05 | 西巴特殊化学品控股有限公司 | Polymerization inhibition of acrylates using blends of nitroxides |
| CN101425560A (en) * | 2008-12-08 | 2009-05-06 | 电子科技大学 | Substrate for flexible organic optoelectric device and preparation thereof |
| CN102295499A (en) * | 2010-06-25 | 2011-12-28 | 中国石油化工股份有限公司 | Polymerization inhibitor for inhibiting polymerization of vinyl compound |
| CN106397182A (en) * | 2016-08-31 | 2017-02-15 | 江苏三蝶化工有限公司 | Polymerization inhibitor for preparation apparatus of acrylic acid |
-
2017
- 2017-02-24 CN CN201710102874.1A patent/CN106905188A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1259114A (en) * | 1997-06-13 | 2000-07-05 | 西巴特殊化学品控股有限公司 | Polymerization inhibition of acrylates using blends of nitroxides |
| CN101425560A (en) * | 2008-12-08 | 2009-05-06 | 电子科技大学 | Substrate for flexible organic optoelectric device and preparation thereof |
| CN102295499A (en) * | 2010-06-25 | 2011-12-28 | 中国石油化工股份有限公司 | Polymerization inhibitor for inhibiting polymerization of vinyl compound |
| CN106397182A (en) * | 2016-08-31 | 2017-02-15 | 江苏三蝶化工有限公司 | Polymerization inhibitor for preparation apparatus of acrylic acid |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109575924A (en) * | 2017-09-29 | 2019-04-05 | 中国石油天然气股份有限公司 | Compound polymerization inhibitor and preparation method thereof |
| CN109575924B (en) * | 2017-09-29 | 2021-01-01 | 中国石油天然气股份有限公司 | Compound polymerization inhibitor and preparation method thereof |
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Application publication date: 20170630 |
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