CN100345804C - High-efficient inhibitor for process of refining phenylethylene and use thereof - Google Patents
High-efficient inhibitor for process of refining phenylethylene and use thereof Download PDFInfo
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- CN100345804C CN100345804C CNB200610065650XA CN200610065650A CN100345804C CN 100345804 C CN100345804 C CN 100345804C CN B200610065650X A CNB200610065650X A CN B200610065650XA CN 200610065650 A CN200610065650 A CN 200610065650A CN 100345804 C CN100345804 C CN 100345804C
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Abstract
The present invention relates to a high-efficient inhibitive substance for a styrene refining process and a using method thereof. The prevent invention adopts a composite inhibitive substance of benzofuran ketone polymer or a monomer of the benzofuran ketone polymer or phosphorous acid fat and an aromatic amine compound is adopted, so the operating time of a styrene device can be effectively prolonged, the yield and the quality of a styrene product can be increased, and the discharge amount of tar of the styrene device is reduced; meanwhile, the present invention has no adverse effects on the processing of consequent products, and a production process of the styrene device can obtain better economic benefits. The inhibitive substance of the present invention has the advantages of favorable polymerization inhibiting effect, low cost, small viscosity and easy use.
Description
Technical field:
The present invention relates to a kind of high-efficiency polymerization inhibitor and using method thereof that is used for process of refining phenylethylene.
Background technology:
Vinylbenzene is the important foundation raw material of petrochemical industry, and purposes is very extensive, is mainly used in to produce styrene series resin and styrene-butadiene rubber(SBR), can be used for industries such as pharmacy, dyestuff, agricultural chemicals and ore dressing in addition.
Vinylbenzene has the character of vinyl olefins, and is reactive extremely strong, and normal temperature down polymerization just can take place, and temperature is high more, and polymerization velocity is fast more.For polymerization losses and the polymerization fouling that reduces styrene monomer in the phenyl ethylene rectification process, guarantee that distillation system normally carries out, must in rectifying, add stopper.
70～nineties of 20th century, the general both at home and abroad stopper that uses nitro-phenolic compound as the phenyl ethylene rectification process, as 2,2, 4-dinitrophenol (DNP), 2,6-dinitrobenzene p-cresol (DNPC), 4,6-dinitrobenzene-2-sec-butyl phenol (DNBP) etc.These belong to retarder, can not prolong induction period in polymerization, can only reduce polymerization velocity, and along with the vinylbenzene prolongation of heat-up time, polymer content slowly rises always; And this class stopper only in hot vinylbenzene solubility property better, easily produce carcinogens in the dissolution process.Therefore, since the nineties in 20th century, true stopper begins on styrene device on probation, as p-ten.-butylcatechol (TBC) and hydroxylamine compound etc.True stopper can prolong the inductive phase of polyreaction, suppresses polymkeric substance and generates, and polymerization inhibition performance obviously is better than retarder, but inductive phase stopper and free radical reaction be consumed, cause stopper to lack work-ing life.
Above-mentioned stopper all is single agent, and function singleness can't satisfy the requirement of phenyl ethylene rectification device long-period stable operation.1994 begin on the phenyl ethylene rectification device on probation to serve new and effective stopper, these stoppers are generally by 2～3 kinds of composite forming of composition, based on azanol class or piperidine derivative, composite with nitrophenyl phenolic compounds, for example, disclose among the patent EP240297 based on the refining stopper of using of three component Compositional type vinylbenzene of azanol class; U.S. UniroyalChemical company discloses a kind of composite as polymerization inhibitors for styrene rectification with piperidine derivative and DNBP, DNPC among the patent US 5545756.The Compositional type stopper has effectively utilized the advantage of retarder and true stopper, because the synergy of each component, the poly-efficient of resistance significantly improves, and the stopper consumption also obviously reduces, and toxicity significantly reduces.Though the stopper gas phase polymerization inhibition effect of these Compositional types is better relatively, also has certain defective, at first azanol class and piperidine derivative compounds price are higher; Secondly these two kinds of compound high temperature are volatile, and the liquid phase polymerization inhibition effect is poor.And prepared stopper kinematic viscosity (is generally 6mm greatly
2About/s), resistance is big, and therefore the energy consumption height has increased cinnamic production cost.
Summary of the invention:
The object of the present invention is to provide a kind of polymerization inhibition effect is good, cost is low, viscosity is little Compositional type stopper and using method thereof, adopt cumarone one monomers or its polymer or phosphorous acid ester and aromatic amine compounds to carry out composite, thereby prolong the working time of styrene device effectively, improve the output and the quality of styrene product, reduce the quantity discharged of styrene device tar, simultaneously subsequent product is processed without any detrimentally affect, made the production process of styrene device obtain better economic benefit.
The invention main points:
The present invention is a kind of high-efficiency polymerization inhibitor that is used for process of refining phenylethylene, form by effective ingredient A component, B component and organic solvent, it is characterized in that: the mass ratio of A component and B component is 0.1～10: 1, be preferably 0.8～2: 1, wherein the A component is selected from benzofuranone or phenylbenzene phosphorous acid ester (ODP); The B component is a kind of in the following material or their mixture: oxamide, N nitrosodiphenyl amine or morpholine.
Said organic solvent is C
5-C
10Hydro carbons, its consumption does not have strict requirement, so that the kinematic viscosity of stopper remains on 1～2mm in the time of 20 ℃
2The scope of/s is for well.
The preparation method of stopper of the present invention is simple, and A component, B component substance are dissolved in the organic solvent, at room temperature stirs to get final product.
The present invention also provides a kind of using method that is used for the high-efficiency polymerization inhibitor of process of refining phenylethylene, and stopper of the present invention is added in the crude styrene material for the treatment of rectifying with the mass concentration that is not less than 1ppm.The mass concentration of stopper in crude styrene consumption preferably is 1～2000ppm; Better consumption is 1～1000ppm; Best consumption is 1～500ppm.
The present invention is producing on the research basis of reason and styrene polymerization mechanism and is obtaining causing styrene polymerization, studies show that the factor aerobic that causes styrene polymerization, metallic impurity, heat etc., and styrene polymerization is followed radical polymerization mechanism.
Styrene monomer can catalysis generate free radical in higher temperature or contacting metal, and quickens the polyreaction process by dual mode.If aerobic exists, free radical and monomer reaction generate peroxy radical, thereby peroxy radical will further generate the more freedom base with monomer reaction.Under the condition of anaerobic, free radical and monomer reaction generate new free radical, and this process can constantly be carried out, and generate the more freedom base.And in case produced free radical, will polymerization reaction take place, number of free radical is high more, and the speed of polyreaction is just fast more.Stopper of the present invention contains the metal passivation composition, can generate stable complex compound with metal ion-chelant, suppresses metal ion and causes the free radical generation; Also contain peace and quiet dispersion component, this composition can be adsorbed on the tiny polymer surfaces that has formed in the material of upstream and form protective membrane, stops polyreaction to continue to take place; The most important thing is that the anti-oxygen inhibition composition that contains in the stopper of the present invention is high temperature resistant, not only can catch peroxy radical, can also combine with alkyl diradical, thereby suppress styrene polymerization effectively.In the stopper of the present invention between two class components synergistic effect obvious, good with media compatibility, without any detrimentally affect, and stopper of the present invention also has the low advantage of cost to subsequent product.
Embodiment:
Under constantly stirring, in mass, (be the commodity row number, major ingredient is C at commercially available 2# solvent
5-C
10Hydro carbons) adds the A component shown in the table 1, B component in respectively, it is mixed, promptly get high-efficiency polymerization inhibitor of the present invention.
Table 1: the component of embodiment 1-10 stopper and proportioning (data in the table are mass fraction)
| Embodiment | The A component | The B component | Organic solvent | |||
| Benzofuranone | ODP | Oxamide | N nitrosodiphenyl amine | Morpholine | The 2# solvent | |
| 1 | 40 parts | 35 parts | 25 parts | |||
| 2 | 40 parts | 30 parts | 30 parts | |||
| 3 | 45 parts | 30 parts | 25 parts | |||
| 4 | 40 parts | 40 parts | 20 parts | |||
| 5 | 35 parts | 40 parts | 25 parts | |||
| 6 | 30 parts | 45 parts | 25 parts | |||
| 7 | 30 parts | 25 parts | 20 parts | 25 parts | ||
| 8 | 20 parts | 20 parts | 35 parts | 25 parts | ||
| 9 | 20 parts | 30 parts | 30 parts | 20 parts | ||
| 10 | 25 parts | 20 parts | 20 parts | 35 parts | ||
The applicating evaluating experiment of embodiment 1 stopper:
The stopper of example 1 joined by 500ppm estimate that (estimating raw material is the crude styrene material that industrial actual fabrication vinylbenzene enters rectifier unit in the raw material, its quality group becomes: 0.6% benzene, 1.8% toluene, 0.2% dimethylbenzene, 42% ethylbenzene, 54% vinylbenzene), in temperature is that 120 ℃, pressure are under the 2.5Mpa condition, after 12 hours, be 1.1mg/100ml according to GB/T 509-88 standard test gum level.
The applicating evaluating experiment of embodiment 2 stoppers:
The stopper of example 2 being joined by 400ppm estimate in the raw material, is that 120 ℃, pressure are under the 2.5Mpa condition in temperature, after 12 hours, is 1.2mg/100ml according to GB/T 509-88 standard test gum level.
The applicating evaluating experiment 1 of embodiment 3 stoppers:
The stopper of example 3 being joined by 300ppm estimate in the raw material, is that 120 ℃, pressure are under the 2.5Mpa condition in temperature, after 12 hours, is 1.25mg/100ml according to GB/T 509-88 standard test gum level.
The applicating evaluating experiment 2 of embodiment 3 stoppers:
The stopper of example 3 being joined by 200ppm estimate in the raw material, is that 120 ℃, pressure are under the 2.5Mpa condition in temperature, after 12 hours, is 1.21mg/100ml according to GB/T 509-88 standard test gum level.
The applicating evaluating experiment of embodiment 5 stoppers:
The stopper of example 5 being joined by 200ppm estimate in the raw material, is that 120 ℃, pressure are under the 2.5Mpa condition in temperature, after 12 hours, is 1.20mg/100ml according to GB/T 509-88 standard test gum level.
The applicating evaluating experiment of embodiment 6 stoppers:
The stopper of example 6 being joined by 200ppm estimate in the raw material, is that 120 ℃, pressure are under the 2.5Mpa condition in temperature, after 12 hours, is 1.22mg/100ml according to GB/T 509-88 standard test gum level.
The applicating evaluating experiment of embodiment 7 stoppers:
The stopper of example 7 being joined by 200ppm estimate in the raw material, is that 120 ℃, pressure are under the 2.5Mpa condition in temperature, after 12 hours, is 1.19mg/100ml according to GB/T 509-88 standard test gum level.
The applicating evaluating experiment of embodiment 8 stoppers:
The stopper of example 8 being joined by 100ppm estimate in the raw material, is that 120 ℃, pressure are under the 2.5Mpa condition in temperature, after 12 hours, is 1.34mg/100ml according to GB/T 509-88 standard test gum level.
Applicating evaluating experiment to embodiment 9 stoppers:
The stopper of example 9 being joined by 50ppm estimate in the raw material, is that 120 ℃, pressure are under the 2.5Mpa condition in temperature, after 12 hours, is 1.41mg/100ml according to GB/T 509-88 standard test gum level.
The applicating evaluating experiment of embodiment 10 stoppers:
The stopper of example 10 being joined by 20ppm estimate in the raw material, is that 120 ℃, pressure are under the 2.5Mpa condition in temperature, after 12 hours, is 1.50g/100ml according to GB/T 509-88 standard test gum level.
Blank contrast experiment
Not adding any stopper in the raw material toward estimating, is that 120 ℃, pressure are under the 2.5Mpa condition in temperature, after 12 hours, is 2.56g/100ml according to GB/T 509-88 standard test gum level.
From the experiment of above applicating evaluating, blank contrast experiment's result as can be seen, use stopper of the present invention after, gum level obviously reduces, and shows that cinnamic polymerization has obtained suppressing effectively, shows that stopper resistance of the present invention gathers.The invention described above obtains stopper and measures according to the method for GB/T265-88 in addition, and kinematic viscosity is 1～2mm in the time of 20 ℃ all
2/ s is starkly lower than the viscosity of the stopper of present employing.Stopper price of the present invention in addition hangs down about 15% approximately than import stopper.
Claims (7)
1. a high-efficiency polymerization inhibitor that is used for process of refining phenylethylene is made up of A component, B component and organic solvent, it is characterized in that: the A component is selected from benzofuranone or phenylbenzene phosphorous acid ester; The B component is a kind of in the following material or their mixture: oxamide, N nitrosodiphenyl amine or morpholine; The mass ratio of A component and B component is 0.1～10: 1.
2. according to the high-efficiency polymerization inhibitor of claim 1, it is characterized in that: the mass ratio of A component and B component is 0.8～2: 1.
3. according to the high-efficiency polymerization inhibitor of claim 1 or 2, it is characterized in that: said organic solvent is C
5-C
10Hydro carbons, its consumption is to make the kinematic viscosity of stopper in the time of 20 ℃ remain on 1～2mm
2The scope of/s.
4. using method that is used for the high-efficiency polymerization inhibitor of process of refining phenylethylene is added into the high-efficiency polymerization inhibitor of claim 1 or 2 or 3 in the crude styrene material with the mass concentration that is not less than 1ppm.
5. according to the using method of claim 4, it is characterized in that: high-efficiency polymerization inhibitor is added in the crude styrene material with the mass concentration of 1～2000ppm.
6. according to the using method of claim 4 or 5, it is characterized in that: high-efficiency polymerization inhibitor is added in the crude styrene material with the mass concentration of 1～1000ppm.
7. according to the using method of claim 6, it is characterized in that: high-efficiency polymerization inhibitor is added in the crude styrene material with the mass concentration of 1～500ppm.
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| CNB200610065650XA CN100345804C (en) | 2006-03-23 | 2006-03-23 | High-efficient inhibitor for process of refining phenylethylene and use thereof |
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|---|---|---|---|
| CNB200610065650XA CN100345804C (en) | 2006-03-23 | 2006-03-23 | High-efficient inhibitor for process of refining phenylethylene and use thereof |
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| CN100345804C true CN100345804C (en) | 2007-10-31 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101440286B (en) * | 2008-11-03 | 2011-03-30 | 淮海工学院 | Compound polymerization inhibitor and uses thereof |
| CN102249842B (en) * | 2010-05-21 | 2014-08-06 | 中国石油化工股份有限公司 | High-efficiency environmentally-friendly polymerization inhibitor of styrene |
| CN103274892B (en) * | 2013-05-31 | 2015-04-22 | 滁州市润达溶剂有限公司 | Method for refining styrene |
| CN104193576B (en) * | 2014-08-08 | 2016-05-25 | 北京斯伯乐科技发展有限公司 | Superpower multi-functional styrene polymerization inhibitor and using method thereof |
| CN105503502B (en) * | 2014-10-14 | 2018-02-13 | 中国石油化工股份有限公司 | The polymerization inhibitor for preventing alkynes from polymerizeing |
| CN107488095A (en) * | 2017-07-17 | 2017-12-19 | 北京斯伯乐科技发展有限公司 | A kind of preparation of environment-friendly type retarder for styrene device and its application method |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1079755A (en) * | 1992-04-23 | 1993-12-22 | 尤尼罗亚尔化学公司 | The stopper of vinyl aromatic compounds |
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2006
- 2006-03-23 CN CNB200610065650XA patent/CN100345804C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1079755A (en) * | 1992-04-23 | 1993-12-22 | 尤尼罗亚尔化学公司 | The stopper of vinyl aromatic compounds |
Non-Patent Citations (2)
| Title |
|---|
| 胺和酚类及其复合阻聚剂在乙烯装置中的应用 张继明，石油炼制与化工，第26卷第8期 1994 * |
| 苯乙烯精馏阻聚剂的应用技术 何仕新，兰化科技，第4卷第2期 1986 * |
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