CN107935886B - Preparation and use method of polymerization inhibitor for acrylonitrile device - Google Patents
Preparation and use method of polymerization inhibitor for acrylonitrile device Download PDFInfo
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- CN107935886B CN107935886B CN201711223739.9A CN201711223739A CN107935886B CN 107935886 B CN107935886 B CN 107935886B CN 201711223739 A CN201711223739 A CN 201711223739A CN 107935886 B CN107935886 B CN 107935886B
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- polymerization inhibitor
- acrylonitrile
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- polymerization
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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
Abstract
An efficient polymerization inhibitor used in the production process of acrylonitrile. The polymerization inhibitor utilizes the synergistic effect of compounds in different classes, greatly improves the polymerization inhibition efficiency of a single component, and can effectively solve related problems caused by scale and dirt deposition by introducing a clean dispersing component and a metal passivation component. The water-soluble efficient polymerization inhibitor can effectively inhibit free radical polymerization and disperse formed scales, so that the scales are uniformly dispersed in material flow, the scales are prevented from being separated out in an acrylonitrile production device, and the production operation period of the device can be prolonged.
Description
Technical Field
The application belongs to the field of acrylonitrile production, and particularly relates to a polymerization inhibitor for an acrylonitrile device refining system and a using method thereof.
Background
Acrylonitrile is a widely used chemical intermediate, and is a basic raw material for synthetic fibers, synthetic rubbers, synthetic plastics, and the like. Acrylonitrile is important in the propylene series, and the production of acrylonitrile is only second in the propylene series less than that of polypropylene worldwide. However, in the production process, the double bond in the structural formula makes the chemical property more active, and chemical reactions such as self-polymerization, copolymerization, hydrolysis and the like can occur. Resulting in a decrease in product yield and polymer deposition in the system, resulting in plugging of heat exchangers, trays and process piping.
Currently, the most common polymerization inhibitor used in acrylonitrile plants is hydroquinone, which is usually added in drying columns, dehydrocyanation columns and finishing columns. However, as (1) hydroquinone is a retarder and has low termination speed for the free radical reaction, more polymers are still generated in the production process, and the hydroquinone is a main factor influencing the long-term operation of an acrylonitrile device. The unit and equipment blockage can cause material loss, device parking and safety and environmental protection problems, and the long-period safe and stable operation of the acrylonitrile device is seriously influenced and restricted. (2) Hydroquinone is solid, needs to be prepared by water on site, has long preparation time due to low solubility, and is easy to cause flying dust in the preparation process to influence the physical health of workers.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a preparation method and a use method of a low-toxicity high-efficiency polymerization inhibitor for an acrylonitrile device refining system. The polymerization inhibitor can completely replace hydroquinone currently used. Compared with hydroquinone, the polymerization inhibitor can quickly inhibit the free radical polymerization of acrylonitrile and effectively prolong the operation time of an acrylonitrile device. The polymerization inhibitor is liquid, can be directly used in industrial fields without preparation, has far lower toxicity than hydroquinone, and belongs to a novel low-toxicity environment-friendly polymerization inhibitor.
The invention is characterized in that:
a low-toxicity high-efficiency polymerization inhibitor for an acrylonitrile device refining system comprises a component A, a component B and a component C. The component A is 2, 5-di-tert-butyl catechol, 2, 6-di-tert-butyl-p-cresol and 2, 6-di-tert-butyl-4-methoxyphenol; the component B is N, N ' -diphenyl-p-phenylenediamine, N, N ' -diethyl-p-phenylenediamine and N, N ' -di-sec-butyl-p-phenylenediamine; the component C is hydroquinone; the balance being solvent. The mass ratio of the component A to the component B to the component C is 5-25: 5-20. The optimal mass ratio is 20-25: 5-10: 10-20. Wherein the component A is preferably 2, 6-di-tert-butyl-4-methoxyphenol; component B is preferably N, N' -di-sec-butyl-p-phenylenediamine, component C is preferably hydroquinone, and the balance is solvent.
The invention also provides a use method of the polymerization inhibitor in an acrylonitrile device refining system, wherein the polymerization inhibitor is injected into the feeding or reflux or tower of a drying/dehydrocyanation/finished product tower and is continuously injected on line, and the added mass concentration is 20-300 ppm, preferably 20-150 ppm, based on the yield of acrylonitrile.
The device is obtained by testing a laboratory and a pilot plant on the basis of researching the principle of forming the dirt in the acrylonitrile plant. Acrylonitrile plants are often accompanied by polymerization reactions in normal production, wherein the polymerization of acrylonitrile by self-polymerization or other reaction by-products such as hydrocyanic acid, acrolein, acrylic acid, acrylamide, etc., can cause fouling problems in the system. In addition, corrosion by-products, catalyst separation, improper use of defoamers, and unstable PH control, which are produced in the system, accelerate the production of system polymers and the deposition of scale. These scales occur mostly in the form of flake or crystalline polymers. The generation of the fouling materials can shorten the operation period of equipment such as a tower, a reboiler, a heat exchanger and the like and reduce the production efficiency. In general, the acrylonitrile polymerization fouling of the drying column, dehydrocyanation column and finishing column is the most severe. The cost of cleaning these foulants is high, sometimes requiring plant shut-down, with significant economic loss to production.
The invention applies the theory of synergistic effect and selects the high-efficiency polymerization inhibitor of a multi-component mixing system with a multifunctional group structure and different vapor pressures. Experiments prove that the polymerization inhibitor has high polymerization inhibition performance in the acrylonitrile rectification process. This is because: in the rectification process of acrylonitrile, gas-liquid phase mass transfer process is adopted, so that the polymerization inhibitor is distributed in the gas phase and the liquid phase of monomer acrylonitrile according to the vapor pressure of the polymerization inhibitor. The polymerization inhibitor with higher vapor pressure prevents gas-phase acrylonitrile from polymerizing; the polymerization inhibitor having a low vapor pressure prevents the polymerization of acrylonitrile in the liquid phase. And the polymerization inhibitor components have synergistic effect under different vapor pressures, so that the polymerization inhibition efficiency of the single component is improved.
The polymerization inhibitor is liquid, can be directly filled without dilution, has far lower toxicity than hydroquinone, and belongs to a low-toxicity and high-efficiency polymerization inhibitor. Has no influence on products and downstream devices, and is safe and environment-friendly to use. Therefore, the invention can bring remarkable economic and social benefits for acrylonitrile devices.
The specific implementation mode is as follows:
the present invention will be described in detail with reference to examples.
Example 1A total reflux operation was carried out on 1000g of acrylonitrile from which the polymerization inhibitor was removed in the following apparatus (operating temperature: 100 ℃ C., time: 30 minutes), 100ppm of the polymerization inhibitor was added, respectively, and then the polymer content in the product was measured to be 3.22 g.
Example 2A total reflux operation was carried out on 1000g of acrylonitrile from which the polymerization inhibitor was removed in the following apparatus (operating temperature: 100 ℃ C., time: 30 minutes), 100ppm of the polymerization inhibitor was added, respectively, and then the polymer content in the product was measured to be 2.86 g.
Example 3A total reflux operation was carried out on 1000g of polymerization inhibitor-removed acrylonitrile in the following apparatus (operating temperature: 100 ℃ C., time: 30 minutes), 100ppm of each polymerization inhibitor was added, and then the polymer content in the product was measured to be 2.14 g.
Example 4A total reflux operation was carried out on 1000g of polymerization inhibitor-removed acrylonitrile in the following apparatus (operating temperature: 100 ℃ C., time: 30 minutes), 100ppm of each polymerization inhibitor was added, and then the polymer content in the product was measured to be 2.23 g.
Example 5A total reflux operation was carried out on 1000g of polymerization inhibitor-removed acrylonitrile in the following apparatus (operating temperature: 100 ℃ C., time: 30 minutes), 100ppm of each polymerization inhibitor was added, and then the polymer content in the product was measured to be 1.98 g.
Example 6A total reflux operation was conducted by taking 1000g of acrylonitrile from which the polymerization inhibitor was removed (operation temperature: 100 ℃ C., time: 30 minutes) in the following apparatus, 100ppm of the polymerization inhibitor was added, respectively, and then the polymer content in the product was measured to be 1.76 g.
Example 7A total reflux operation was conducted by taking 1000g of acrylonitrile from which the polymerization inhibitor was removed (operation temperature: 100 ℃ C., time: 30 minutes) in the following apparatus, 100ppm of the polymerization inhibitor was added, respectively, and then the polymer content in the product was measured to be 2.37 g.
Example 8A total reflux operation was conducted by taking 1000g of acrylonitrile from which the polymerization inhibitor was removed (operation temperature: 100 ℃ C., time: 30 minutes) in the following apparatus, 100ppm of the polymerization inhibitor was added, respectively, and then the polymer content in the product was measured to be 2.86 g.
Example 9A total reflux operation was conducted by taking 1000g of acrylonitrile from which the polymerization inhibitor was removed (operation temperature: 100 ℃ C., time: 30 minutes) in the following apparatus, 100ppm of the polymerization inhibitor was added, respectively, and then the polymer content in the product was measured to be 2.12 g.
Comparative example 1A total reflux operation was carried out on 1000g of acrylonitrile from which the polymerization inhibitor was removed (operating temperature: 100 ℃ C., time: 30 minutes) in an apparatus to which 100ppm of polymerization inhibitor M was added, respectively, and then the polymer content in the product was measured to be 1.76 g.
Comparative example 2A total reflux operation was carried out on 1000g of acrylonitrile from which the polymerization inhibitor was removed (operating temperature: 100 ℃ C., time: 30 minutes) in an apparatus to which 100ppm of the polymerization inhibitor A was added from a foreign country, respectively, and then the polymer content in the product was measured to be 1.89 g.
Comparative example 3A total reflux operation was carried out on 1000g of acrylonitrile from which the polymerization inhibitor was removed (operating temperature: 100 ℃ C., time: 30 minutes) in an apparatus to which 100ppm of the polymerization inhibitor B was added from a foreign country, respectively, and then the polymer content in the product was measured to be 2.11 g.
Comparative example 4A total reflux operation was carried out on 1000g of acrylonitrile from which the polymerization inhibitor was removed (operating temperature: 100 ℃ C., time: 30 minutes) in an apparatus to which 100ppm of hydroquinone as the polymerization inhibitor was added, respectively, and then the polymer content in the product was measured to be 3.12 g.
| Comparative example | Polymerization inhibitor | Addition amount of ppm | Polymer g |
| 1 | This patent product M | 100 | 1.76 |
| 2 | Foreign polymerization inhibitor A | 100 | 1.89 |
| 3 | Foreign polymerization inhibitor B | 100 | 2.11 |
| 4 | Hydroquinone | 100 | 3.12 |
As can be seen from the examples and the comparative examples of foreign products, the product of the patent is superior to hydroquinone and foreign imported products under the same concentration.
Effect of polymerization inhibitor on polymer at different concentrations:
by testing the influence of the polymerization inhibitor at different concentrations on the polymer, it can be seen that the polymer still has a downward trend after the total amount of the polymerization inhibitor exceeds 150ppm, but the polymer is not obvious, and the optimal use concentration is 50-150 ppm in consideration of the production and operation cost of an acrylonitrile device.
Toxicity data comparison table
As can be seen from the comparative data of the toxicity on the table above, the product of the patent belongs to a low-toxicity environment-friendly product.
Claims (4)
1. A polymerization inhibitor applied to an acrylonitrile device product refining system comprises a component A, a component B, a component C and a solvent, wherein the component A is 2, 6-di-tert-butyl-4-methoxyphenol; the component B is N, N' -di-sec-butyl p-phenylenediamine, and the component C is hydroquinone; and (2) component A: and (B) component: and (3) component C: the mass ratio is 20: 10, and the balance is solvent.
2. The polymerization inhibitor according to claim 1, wherein the solvent is C8-C10An aromatic hydrocarbon.
3. The method of claim 1, wherein the polymerization inhibitor is continuously injected into the acrylonitrile plant on-line, and the injection concentration is 20 to 300ppm based on the acrylonitrile yield.
4. The use method according to claim 3, wherein the injection concentration is 50 to 150 ppm.
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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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| CN201711223739.9A CN107935886B (en) | 2017-11-29 | 2017-11-29 | Preparation and use method of polymerization inhibitor for acrylonitrile device |
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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 |
|---|
| 丙烯腈阻聚剂的研究;张自义 等;《合成橡胶工业》;19821231;第6卷(第4期);第307-308页 * |
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