CN1254458C - Quenching oil viscosity breaking agent in cracking fractionator - Google Patents
Quenching oil viscosity breaking agent in cracking fractionator Download PDFInfo
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- CN1254458C CN1254458C CN 03137612 CN03137612A CN1254458C CN 1254458 C CN1254458 C CN 1254458C CN 03137612 CN03137612 CN 03137612 CN 03137612 A CN03137612 A CN 03137612A CN 1254458 C CN1254458 C CN 1254458C
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Abstract
The present invention relates to the preparation of viscosity reductant of quenching oil in a schizolysis and fractionation device. Viscosity reductant which is suitable for various technological conditions of an ethylene devices is prepared from a polymerization inhibitor and a dispersing agent in the weight proportion of 1: 0.1 to 10; the dispersing agent is 2-succinimide prepared from 1000 to 3000 polyisobutylene; the polymerization inhibitor is prepared from a santonox r antioxidant and a phosphite antioxidant in the weight proportion of 1: 0.1 to 8.100 to 5000 ppm of viscosity reductant is added at the bottom of a quenching oil column, and thus, the viscidity increase of quenching oil can be effectively controlled; the viscosity reductant which can not cause the emulsification of quenching water in the system can decelerate the fouling of equipment in a quenching system of schizolysis device for ethene.
Description
Technical field
The present invention relates to Control Circulation quench oil viscosity reductant in the ethylene cracker, particularly be fit to the preparation of the efficient viscosity depressant of various ethylene unit processing condition.
Background technology
In the cracking of ethylene production process, petroleum naphtha, thermo-cracking takes place in lighter hydrocarbons etc. between 750～850 ℃, and split product is cooled to 350～450 ℃ rapidly in the pyrolyzer outlet.Mix with quench oil circulated to be cooled to about 220 ℃ then and send into quenching oil column.Isolating the light component of carbon below 9 from the quenching oil cat head, is the heavy component of carbon more than 9 at the bottom of the tower.A part of material at the bottom of the quenching oil column is circulated in the charging of quenching oil column.Owing to contain unsaturated aromatic hydrocarbons such as vinylbenzene, indenes in the charging of quenching oil column, polymerization at high temperature can take place in them, generates macromolecular substance and causes quenching oil constantly to raise recycling medium viscosity.Increase the power of recycle pump, reduced the heat exchange efficiency of quenching oil.
Traditional method is that the quench oil circulated slip-stream is mixed with part pyrolyzer effluent, separates to obtain steam and liquid, and steam is back to fractionator, and discharges the liquid of the oily product that acts as a fuel, and reduces the viscosity of quench oil circulated.For example the control method of quenching oil viscosity is in the cracking fractionation plant described in the patent CN1220987A, make of the quenching oil slip-stream mixing contact of pyrolyzer effluent with 0.1～0.5kg/kg, separate the vapour-liquid mixture that obtains, remove tarry liquid, improve quench oil circulated viscosity.Control the chilling oil viscosity by this way and can significantly increase production cost and process cost.Also having method is to introduce the viscosity that low viscous material reduces quench oil circulated in system, be 300～370 low viscosity component for example by in quench oil circulated, constantly adding boiling range, keep the viscosity of quench oil circulated, this mode is controlled the chilling oil viscosity can increase production cost and process cost equally.
At present external companies are as Exxon, Nalco company, suppress the growth of quenching oil viscosity by adding viscosity depressant, obtained effect preferably, but because the difference of processing condition, limited the widespread use of its viscosity depressant, especially do not seen at home and used on the ethylene unit.
Summary of the invention
The object of the invention is to provide quench oil viscosity reductant in a kind of cracking fractionator by different technology conditions quenching oil viscosity being increased the research of the mechanism of action of reason and viscosity depressant, can be fit to the efficient viscosity depressant of various ethylene unit processing condition.
The present invention is achieved in that
Viscosity depressant of the present invention is formulated by stopper and dispersion agent, and the part by weight of dispersion agent and stopper is 1: 0.1～8, preferred 1: 0.5～6, most preferably 1: 1～3.
Stopper of the present invention is formulated by Hinered phenols antioxidant and phosphite ester kind antioxidant.The part by weight of Hinered phenols antioxidant and phosphite ester kind antioxidant is 1: 0.1～10, preferred 1: 0.5～7, most preferably 1: 1～4.
Hinered phenols antioxidant of the present invention can be 2,6-di-t-butyl-4-ethylphenol, 2,6-di-t-butyl-4-normal-butyl phenol, 2, [3-(3 for 2 ｀-thiobis, the 5-di-tert-butyl-hydroxy phenyl) ethyl propionate], four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, β-(4-hydroxyl-3, the 5-di-tert-butyl-phenyl) the positive octadecanol ester of propionic acid, 6,6-di-t-butyl-2,2 ｀-sulfo-two-right-cresylol, 2,4-dimethyl 6-tert.-butyl phenol, styrenated phenol, butylation octyl group phenol, a kind of material in the butylation vinylbenzene cresols or the mixture of several materials.
Phosphite ester kind antioxidant of the present invention can be three (2, the 4-di-tert-butyl-phenyl) a kind of material in phosphorous acid ester, three-(nonyl phenyl) phosphorous acid ester, tetramethylolmethane diphosphite two (2, the 4-di-tert-butyl-phenyl) ester, triphenyl phosphite, tricresyl phosphite second monooctyl ester, trilauryl trithiophosphite, phosphorous acid two lauryls, trilauryl phosphite, isooctyl diphenyl phosphite, phosphorous acid hexichol isodecyl ester, the phosphorous acid triphen isodecyl ester or the mixture of several materials.
Dispersion agent of the present invention is to be two succimides of 1000～3000 polyisobutene preparation by molecular weight.
The add-on of viscosity depressant of the present invention is 100～5000ppm, and viscosity depressant can not cause the emulsification of quenched water in the system, the fouling that can slow down equipment in the ethylene cracker quenching system simultaneously.
The invention has the advantages that:
Adopt the viscosity depressant of the present invention's preparation can suppress the growth of quench oil circulated viscosity simply and effectively, and cost is lower.Increase by at the bottom of quenching oil column, adding viscosity depressant control chilling oil viscosity, the fouling that can slow down equipment in the ethylene cracker quenching system simultaneously, thus improve the thermo-efficiency of quench oil circulated, improve the separating effect of quenching oil column.The adding of viscosity depressant can not produce any detrimentally affect to the technological operation of ethylene cracker quenching system, particularly can not cause the emulsification of quenched water in the system.
Embodiment
Following example is to further specify of the present invention.
Example 1
The preparation of viscosity depressant: Hinered phenols antioxidant selects 2,6-di-t-butyl-4-ethylphenol, phosphite ester kind antioxidant selects three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester is that 1: 5 ratio uniform mixing is mixed with stopper with Hinered phenols antioxidant and phosphite ester kind antioxidant by weight.It is two succimides of 1500 that dispersion agent is selected the molecular weight of polyisobutene, is that 1: 4 ratio uniform mixing is mixed with viscosity depressant by weight with dispersion agent and stopper.
Quenching oil sample 250 is restrained in the 500ml four-hole bottle of packing into, add viscosity depressant 1000ppm of the present invention, on four-hole bottle, install electronic stirring and prolong additional, avoid raising owing to the quenching oil change of component causes quenching oil viscosity.Be heated to 225 ℃ of constant temperature 12 hours, sampling in per 4 hours is once measured the kinematic viscosity of quenching oil sample.Experimental result is as shown in table 1.
Example 2
The preparation of viscosity depressant: Hinered phenols antioxidant selects 2,6-di-t-butyl-4-ethylphenol and β-(4-hydroxyl-3, the 5-di-tert-butyl-phenyl) weight ratio of the positive octadecanol ester of propionic acid is 1: 2 a mixture, phosphite ester kind antioxidant selects three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester is that 1: 5 ratio uniform mixing is mixed with stopper with Hinered phenols antioxidant and phosphite ester kind antioxidant by weight.It is two succimides of 1500 that dispersion agent is selected the molecular weight of polyisobutene, is that 1: 4 ratio uniform mixing is mixed with viscosity depressant by weight with dispersion agent and stopper.
Quenching oil sample 250 is restrained in the 500ml four-hole bottle of packing into, add viscosity depressant 1000ppm of the present invention, on four-hole bottle, install electronic stirring and prolong additional, avoid raising owing to the quenching oil change of component causes quenching oil viscosity.Be heated to 225 ℃ of constant temperature 12 hours, sampling in per 4 hours is once measured the kinematic viscosity of quenching oil sample.Experimental result is as shown in table 1.
Comparative Examples 1
Quenching oil sample 250 is restrained in the 500ml four-hole bottle of packing into, add the viscosity depressant 1000ppm of Nalco company, on four-hole bottle, install electronic stirring and prolong additional, avoid raising owing to the quenching oil change of component causes quenching oil viscosity.Be heated to 225 ℃ of constant temperature 12 hours, sampling in per 4 hours is once measured the kinematic viscosity of quenching oil sample.Experimental result is as shown in table 1.
Comparative Examples 2
Quenching oil sample 250 is restrained in the 500ml four-hole bottle of packing into,, on four-hole bottle, install electronic stirring and prolong additional, avoid raising owing to the quenching oil change of component causes quenching oil viscosity not with viscosity depressant.Be heated to 225 ℃ of constant temperature 12 hours, sampling in per 4 hours is once measured the kinematic viscosity of quenching oil sample.Experimental result sees Table l.
We are as can be seen under experimental temperature from last table, and using viscosity depressant of the present invention that the chilling oil viscosity is increased has significant inhibitory effect.Because the kinetics aspect, the visbreaking effect of viscosity depressant is more obvious in the device at the scene.
Example 5
Though the operation controlled temperature of quench oil circulated is no more than 220 ℃, in the actual mechanical process of device, quench oil circulated can contact with 450 ℃ cracking mixing of materials, so viscosity depressant need have certain high temperature stability.We have examined or check the high temperature stability performance of viscosity depressant of the present invention by differential scanning calorimeter.The heat decomposition temperature that records viscosity depressant is 345 ℃.
We as can be seen, the heat decomposition temperature of viscosity depressant is much higher than the operation controlled temperature of quench oil circulated, so we can suitably improve the service temperature of quenching oil Tata still in the apparatus system, thus the light constituent yield of raising quenching oil column, the economic benefit of increase device.
Example 6
Because splitting gas component complexity, and in quenching system, there is the separation problem of pyrolysis gasoline and water, thus the introducing of any additives component, comprising metal ion, the introducing of surfactant all may cause oil-water emulsion.Therefore viscosity depressant particularly need cause our attention to the influence of quenching system to the influence of oil-water emulsion.
In the 100ml graduated cylinder, add 40ml pyrolysis gasoline and 40ml water, in pyrolysis gasoline, drip the viscosity depressant of 1000ppm, graduated cylinder is put into the water bath with thermostatic control of 82 ℃ (service temperatures of quenching system oily water separation) and heated 20min.Use electronic stirring rake vigorous stirring 10min, the record water-oil interface.Experimental result sees Table 2.
From table 2 we as can be seen, the adding of viscosity depressant to the oil-water emulsion of quenching system without any influence.
Table 1
| Viscosity depressant | Kinematic viscosity (0 hour) | Kinematic viscosity (4 hours) | Kinematic viscosity (8 hours) | Kinematic viscosity (12 hours) | |
| Example 1 | The present invention | 350mm 2/s | 513mm 2/s | 600mm 2/s | 664mm 2/s |
| Example 2 | The present invention | 350mm 2/s | 503mm 2/s | 590mm 2/s | 654mm 2/s |
| Comparative Examples 1 | Nalco company | 350mm 2/s | 535mm 2/s | 630mm 2/s | 698mm 2/s |
| Comparative Examples 2 | Do not have | 350mm 2/s | 555mm 2/s | 653mm 2/s | 713mm 2/s |
Table 2
| Before viscosity depressant adds | After viscosity depressant adds | |
| Oil reservoir/cm | 40 is transparent | 40 is transparent |
| Water layer/cm | 40 is transparent | 40 is transparent |
| Oily water separation time/s | 20 | 20 |
| Emulsion layer/cm | 0 | 0 |
| State of interface | The interface is clear | The interface is clear |
Claims (3)
1. quench oil viscosity reductant in the cracking fractionator, it is characterized in that: formulated by stopper and dispersion agent, the part by weight of dispersion agent and stopper is 1: 0.1～8, wherein dispersion agent is to be two succimides of 1000～3000 polyisobutene preparation by molecular weight, stopper is formulated by Hinered phenols antioxidant and phosphite ester kind antioxidant, and the part by weight of Hinered phenols antioxidant and phosphite ester kind antioxidant is 1: 0.1～10.
2. according to quench oil viscosity reductant in the claim 1 cracking fractionator, it is characterized in that: Hinered phenols antioxidant is 2,6-di-t-butyl-4-ethylphenol, 2,6-di-t-butyl-4-normal-butyl phenol, 2, [3-(3 for 2 ｀-thiobis, the 5-di-tert-butyl-hydroxy phenyl) ethyl propionate], four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, β-(4-hydroxyl-3, the 5-di-tert-butyl-phenyl) the positive octadecanol ester of propionic acid, 6,6-di-t-butyl-2,2 ｀-sulfo-two-right-cresylol, 2,4 dimethyl 6 tert butyl phenol, styrenated phenol, butylation octyl group phenol, a kind of material in the butylation vinylbenzene cresols or the mixture of several materials.
3. according to quench oil viscosity reductant in the cracking fractionator described in the claim 1, it is characterized in that: phosphite ester kind antioxidant is three (2, the 4-di-tert-butyl-phenyl) a kind of material in phosphorous acid ester, three-(nonyl phenyl) phosphorous acid ester, tetramethylolmethane diphosphite two (2, the 4-di-tert-butyl-phenyl) ester, triphenyl phosphite, tricresyl phosphite second monooctyl ester, trilauryl trithiophosphite, phosphorous acid two lauryls, trilauryl phosphite, isooctyl diphenyl phosphite, phosphorous acid hexichol isodecyl ester, the phosphorous acid triphen isodecyl ester or the mixture of several materials.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03137612 CN1254458C (en) | 2003-06-18 | 2003-06-18 | Quenching oil viscosity breaking agent in cracking fractionator |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03137612 CN1254458C (en) | 2003-06-18 | 2003-06-18 | Quenching oil viscosity breaking agent in cracking fractionator |
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| CN1566042A CN1566042A (en) | 2005-01-19 |
| CN1254458C true CN1254458C (en) | 2006-05-03 |
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| CN 03137612 Expired - Fee Related CN1254458C (en) | 2003-06-18 | 2003-06-18 | Quenching oil viscosity breaking agent in cracking fractionator |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101445749B (en) * | 2008-10-31 | 2012-07-25 | 浙江杭化科技有限公司 | Anti-tartar detersive for quenching oil column of ethylene unit |
| CN101838058B (en) * | 2009-12-31 | 2012-07-18 | 上海良田化工有限公司 | Scale inhibitor of ethylene device process water system and using method thereof |
| US9505988B2 (en) | 2011-10-19 | 2016-11-29 | Nalco Company | Circulation aid for primary fractional quench loops |
| CN106699598B (en) * | 2016-11-18 | 2019-03-01 | 北京誉天利化工有限公司 | A kind of water soluble disperse antisludging agent and its application |
| CN108690622A (en) * | 2018-07-25 | 2018-10-23 | 北京斯伯乐科学技术研究院 | The preparation of ethylene unit quenching oil column viscosity reductant and its application method |
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