CN101838522A - Quenching oil viscosity depressant and use thereof - Google Patents
Quenching oil viscosity depressant and use thereof Download PDFInfo
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- CN101838522A CN101838522A CN200910248005A CN200910248005A CN101838522A CN 101838522 A CN101838522 A CN 101838522A CN 200910248005 A CN200910248005 A CN 200910248005A CN 200910248005 A CN200910248005 A CN 200910248005A CN 101838522 A CN101838522 A CN 101838522A
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Abstract
The invention discloses a quenching oil viscosity depressant, which comprises a polymerization inhibitor, a vehicle and a varsol, wherein the polymerization inhibitor is one or more of 2,2,6,6-tetramethylpiperidine-N-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-oxo-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-amino-2,2,6,6-tetramethylpiperidine-N-oxyl, 4- acetoxy-2,2,6,6-tetramethylpiperidine-N-oxyl and 4-dimethylamino-2,2,6,6-tetramethylpiperidine-N-oxyl. The invention also discloses the use of the quenching oil viscosity depressant. The quenching oil viscosity depressant of the invention can effectively prevent the polymerization of unsaturated compounds in quenching oil. Compared with the conventional quenching oil viscosity depressant, the quenching oil viscosity depressant can greatly reduce the viscosity of the quenching oil under the same conditions and is favorable for improving the heat conductivity of the quenching oil.
Description
Technical field
The present invention is specifically related to a kind of quench oil viscosity reductant and application thereof.
Background technology
Quenching oil in the middle of the ethylene unit is kind of a thermal barrier, and it can cool off the splitting gas of pyrolyzer outlet on the one hand; Can heat dilution steam generation producer generation dilution steam generation on the other hand again, reclaim the heat of splitting gas, reduce the process water discharging.
When quench oil system was normally moved, quenching oil viscosity generally should be controlled at 1500mm
2Below/the s (50 ℃).If quenching oil viscosity surpasses 1500mm
2/ s will make its heat transfer property variation, can not heat dilution steam generation producer generation dilution steam generation effectively, is unfavorable for reducing the process water quantity discharged.Quenching oil viscosity is big in addition, can influence the operational efficiency of quenching oil recycle pump.In a word, quenching oil viscosity is too high is unfavorable for the ethylene unit energy-saving and emission-reduction.
Multiple reduction quenching oil method of viscosity has been proposed both at home and abroad.For example WO99/41328 discloses a kind of viscosity depressant, and this viscosity depressant main component is monoalkyl resinox or many alkyl resinox or the mixture between them.This resin molecular-weight average is 1000-30000, and at least one alkyl has 4-24 carbon atom, alkyl can be straight chain or side chain.The main component of the disclosed viscosity depressant of US5824829 be alkyl benzene sulphonate (ABS) (salt) with arylamine, phenols, hydroquinones in the mixture of one or more materials.The described viscosity depressant of US6096188 then is made up of the mixture of one or several materials in alkylphenol, alkyl diphenol, alkyl connection phenol, arylamine, the nitro oxide.CN1566042A proposes to prepare a kind of viscosity depressant by stopper and dispersion agent, and wherein stopper is made up of Hinered phenols antioxidant and phosphite ester kind antioxidant, and dispersion agent is that molecular weight is two succimides of the polyisobutene preparation of 1000-3000.CN101062880A has described a kind of quench oil viscosity reductant of being made up of stopper, dispersion agent and metallic ion passivation agent, wherein stopper is made up of phenolic antioxidant and amine antioxidants, dispersion agent is made up of polyalkenyl succsinic acid imide etc., and the metallic ion passivation agent is made up of poly-alkylsiloxane etc.The disclosed viscosity depressant of the patent CN1715380A of our company is by stopper and unfold agent and be prepared from, and wherein stopper is selected from one or more in pyrocatechol, sec-Octyl phenol, p-tert-butylphenol, p-ten.-butylcatechol, the Ursol D.
The stopper that above-mentioned viscosity depressant in one's power adopts all is stable molecule, and its mechanism of action is:
The R free radical, the AH stopper.
A compares with R and will stablize, and is difficult for causing new chainpropagation, goes down but free radical A also can continue reaction, that is:
This is a homeostasis process, and the equilibrated result is that most free radicals are in A condition in the medium, and the minority free radical is in R ' state, thereby can only be hindered poly-result relatively.
Because this class stopper is difficult to rapid Mulberry Extract, realize chain termination, the unsaturated compound in the middle of the quenching oil also can polymerization, and the quenching oil molecular-weight average also can increase, and viscosity also can correspondingly increase, and influences its heat transfer property.
Summary of the invention
Technical problem to be solved by this invention is also can polymerization in order to overcome in the existing quench oil viscosity reductant when using the unsaturated compound in the middle of the quenching oil, the quenching oil molecular-weight average also can increase, viscosity also can correspondingly increase, influence defectives such as its heat transfer property, and a kind of quench oil viscosity reductant and application thereof are provided.Quench oil viscosity reductant of the present invention can effectively stop the unsaturated polymerizable compound in the quenching oil, compares with existing quench oil viscosity reductant, under equal conditions can reduce quenching oil viscosity greatly, helps improving its heat transfer property.
The inventor finds, in quench oil viscosity reductant, is stopper with the stable free radical compounds of a class, rapidly Mulberry Extract.As follows:
Wherein, R is the free free radical in the quenching oil, and I is a stopper.This reaction is exceedingly fast, and is reversible hardly, use up the central free radical of medium thereby catch basically, reached than the poly-purpose of resistance more completely.By this class stopper with unfold the viscosity depressant that agent is prepared from and under equal conditions can reduce quenching oil viscosity greatly, help improving its heat transfer property.
Therefore the present invention relates to a kind of quench oil viscosity reductant, it comprises stopper, unfolds agent and varsol; Wherein, described stopper is a nitroxyl free radical, and preferable is 2,2,6,6-tetramethyl--piperidine NO free radical, 4-hydroxyl-2,2,6,6-tetramethyl--piperidine NO free radical, 4-oxo-2,2,6,6-tetramethyl--piperidine NO free radical, 4-amino-2,2,6,6-tetramethyl--piperidine NO free radical, 4-acetoxyl group-2,2,6,6-tetramethyl--piperidine NO free radical and 4-dimethylamino-2,2,6, one or more in the nitroxyl free radical such as 6-tetramethyl--piperidine NO free radical.
Preferable, described quench oil viscosity reductant by stopper, unfold agent and varsol is formed.Wherein, the kind of stopper is ditto described.
Among the present invention, the 5-60% that is weight percentage that the content of described stopper is preferable, that better is 5-30%.
Among the present invention, described unfold agent preferable be selected from trimethyl phosphite 99, triethyl phosphate, tributyl phosphate, di (isooctyl) phosphate, triphenylphosphate, dibutyl phosphite, phosphorous acid benzene di-isooctyl and the triphenyl phosphite one or more; Unfold the preferable 10-60% that is weight percentage of content of agent, that better is 10-50%.
Among the present invention, described varsol is preferable be selected from kerosene, diesel oil, 200# solvent and raffinate oil in one or more; The content of varsol preferable for supplying surplus to weight percent 100%.
The preparation method of quench oil viscosity reductant of the present invention is for getting final product simple mixing of above-mentioned each composition.
The invention still further relates to the application of above-mentioned quench oil viscosity reductant in control chilling oil viscosity.Wherein, that the interpolation concentration of quench oil viscosity reductant is preferable is the 5-100ppm of quenching oil internal circulating load, and that better is 5-20ppm, can extremely effectively control the chilling oil viscosity and rise in the temperature range of the normal operation of ethylene apparatus quench oil tower in this scope.
Except that specified otherwise, raw material that the present invention relates to and reagent are all commercially available to be got.
Positive progressive effect of the present invention is: quench oil viscosity reductant of the present invention can effectively stop the unsaturated polymerizable compound in the quenching oil, compare with existing quench oil viscosity reductant, under equal conditions can reduce quenching oil viscosity greatly, help improving its heat transfer property.
Embodiment
Further specify the present invention with embodiment below, but the present invention is not limited.
Embodiment 1
Stopper is selected 4-hydroxyl-2,2,6,6-tetramethyl--piperidine NO free radical, unfold agent and select triphenylphosphate, solvent is selected the 200# solvent, with stopper 30%, unfold agent 20% and solvent 50% and put into vessel in heating and stir, after being cooled to room temperature, filter to get filtrate, promptly get sample.
On the 1000ml four-hole boiling flask, install electronic stirring, prolong and thermometer additional, add the quenching oil sample that 400g fetches from ethylene unit, add above-mentioned viscosity depressant 50ppm again, 215 ℃ of following constant temperature 24 hours, sampling is then measured kinematic viscosity down at 80 ℃, and test-results is as shown in table 1.
Embodiment 2
Stopper is selected 4-amino-2,2,6,6-tetramethyl--piperidine NO free radical, unfold agent and select dibutyl phosphite, solvent is selected the 200# solvent, with stopper 35%, unfold agent 15% and solvent 50% and put into vessel in heating and stir, after being cooled to room temperature, filter to get filtrate, promptly get sample.
Install electronic stirring, prolong and thermometer additional on the 1000ml four-hole boiling flask, add 400g quenching oil sample, add above-mentioned viscosity depressant 50ppm again, 215 ℃ of following constant temperature 24 hours, sampling was then measured kinematic viscosity down at 80 ℃, and test-results is as shown in table 1.
Comparative Examples 1
Stopper is selected Ursol D, unfolds agent and selects triphenylphosphate, and solvent is selected the 200# solvent, with stopper 30%, unfold agent 20% and solvent 50% and put into vessel in heating and stir, be cooled to room temperature after, filter and promptly get sample.
Install electronic stirring, prolong and thermometer additional on the 1000ml four-hole boiling flask, add 400g quenching oil sample, add above-mentioned viscosity depressant 50ppm again, 215 ℃ of following constant temperature 24 hours, sampling was then measured kinematic viscosity down at 80 ℃, and test-results is as shown in table 1.
Comparative Examples 2
Stopper is selected pyrocatechol and sec-Octyl phenol, unfolds agent and selects dibutyl phosphite, and solvent is selected the 200# solvent, with stopper 35%, unfold agent 15% and solvent 50% and put into vessel in heating and stir, be cooled to room temperature after, filter and promptly get sample.
Install electronic stirring, prolong and thermometer additional on the 1000ml four-hole boiling flask, add 400g quenching oil sample, add above-mentioned viscosity depressant 50ppm again, 215 ℃ of following constant temperature 24 hours, sampling was then measured kinematic viscosity down at 50 ℃, and test-results is as shown in table 1.
The viscosity data of table 1 embodiment and Comparative Examples
| Viscosity depressant | Kinematic viscosity/mm 2/s | |
| Embodiment 1 | The present invention | ??320.3 |
| Comparative Examples 1 | The CN1715380A invention | ??836.6 |
| Embodiment 2 | The present invention | ??468.5 |
| Comparative Examples 2 | The CN1715380A invention | ??935.0 |
As shown in Table 1, the viscosity depressant according to the present invention's preparation has better visbreaking effect than the viscosity depressant that the CN1715380A invention prepares.Also like this in the industrialized unit result of appraisal, more can satisfy ethylene unit to the viscosity depressant performance demands.
Embodiment 3
Stopper selects 2,2,6,6-tetramethyl--piperidine NO free radical, unfold agent and select phosphorous acid benzene di-isooctyl, solvent is selected kerosene, with stopper 5%, unfold agent 60% and solvent 35% and put into vessel in heating and stir, after being cooled to room temperature, filter to get filtrate, promptly get sample.
Install electronic stirring, prolong and thermometer additional on the 1000ml four-hole boiling flask, add 400g quenching oil sample, add above-mentioned viscosity depressant 5ppm again, 215 ℃ of following constant temperature 24 hours, sampling was then measured kinematic viscosity down at 50 ℃, and test-results is as shown in table 2.
Embodiment 4
Stopper is selected 4-oxo-2,2,6,6-tetramethyl--piperidine NO free radical, unfold agent and select triphenyl phosphite, solvent is selected diesel oil, with stopper 60%, unfold agent 10% and solvent 30% and put into vessel in heating and stir, after being cooled to room temperature, filter to get filtrate, promptly get sample.
Install electronic stirring, prolong and thermometer additional on the 1000ml four-hole boiling flask, add 400g quenching oil sample, add above-mentioned viscosity depressant 5ppm again, 215 ℃ of following constant temperature 24 hours, sampling was then measured kinematic viscosity down at 50 ℃, and test-results is as shown in table 2.
Embodiment 5
Stopper selects 2,2,6,6-tetramethyl--piperidine NO free radical, unfold agent and select the phosphorous acid di-isooctyl, solvent is selected to raffinate oil, with stopper 5%, unfold agent 60% and solvent 35% and put into vessel in heating and stir, after being cooled to room temperature, filter to get filtrate, promptly get sample.
Install electronic stirring, prolong and thermometer additional on the 1000ml four-hole boiling flask, add 400g quenching oil sample, add above-mentioned viscosity depressant 100ppm again, 215 ℃ of following constant temperature 24 hours, sampling was then measured kinematic viscosity down at 50 ℃, and test-results is as shown in table 2.
Embodiment 6
Stopper is selected 4-oxo-2,2,6,6-tetramethyl--piperidine NO free radical, unfold agent and select tributyl phosphate, solvent is selected to raffinate oil, with stopper 60%, unfold agent 10% and solvent 30% and put into vessel in heating and stir, after being cooled to room temperature, filter to get filtrate, promptly get sample.
Install electronic stirring, prolong and thermometer additional on the 1000ml four-hole boiling flask, add 400g quenching oil sample, add above-mentioned viscosity depressant 100ppm again, 215 ℃ of following constant temperature 24 hours, sampling was then measured kinematic viscosity down at 50 ℃, and test-results is as shown in table 2.
The viscosity data of table 2 embodiment 3-6
| Kinematic viscosity/mm 2/s | |
| Embodiment 3 | ??680.2 |
| Embodiment 4 | ??634.5 |
| Embodiment 5 | ??355.6 |
| Embodiment 6 | ??287.3 |
As shown in Table 2, use its visbreaking effect of viscosity depressant of the present invention's preparation preferable, the viscosity that is measured to all is lower than 700mm
2/ s.
Claims (10)
1. quench oil viscosity reductant, it is characterized in that: it comprises stopper, unfolds agent and varsol; Wherein, described stopper is a nitroxyl free radical.
2. quench oil viscosity reductant as claimed in claim 1, it is characterized in that: described stopper is 2,2,6,6-tetramethyl--piperidine NO free radical, 4-hydroxyl-2,2,6,6-tetramethyl--piperidine NO free radical, 4-oxo-2,2,6,6-tetramethyl--piperidine NO free radical, 4-amino-2,2,6,6-tetramethyl--piperidine NO free radical, 4-acetoxyl group-2,2,6,6-tetramethyl--piperidine NO free radical and 4-dimethylamino-2,2,6, one or more in 6-tetramethyl--piperidine NO free radical.
3. quench oil viscosity reductant as claimed in claim 1 or 2 is characterized in that: the content of the described stopper 5-60% that is weight percentage.
4. quench oil viscosity reductant as claimed in claim 3 is characterized in that: the content of the described stopper 5-30% that is weight percentage.
5. quench oil viscosity reductant as claimed in claim 1 or 2 is characterized in that: describedly unfold agent and be selected from trimethyl phosphite 99, triethyl phosphate, tributyl phosphate, di (isooctyl) phosphate, triphenylphosphate, dibutyl phosphite, phosphorous acid benzene di-isooctyl and the triphenyl phosphite one or more.
6. quench oil viscosity reductant as claimed in claim 1 or 2 is characterized in that: described content of the unfolding agent 10-60% that is weight percentage.
7. quench oil viscosity reductant as claimed in claim 6 is characterized in that: described content of the unfolding agent 10-50% that is weight percentage.
8. quench oil viscosity reductant as claimed in claim 1 or 2 is characterized in that: described varsol be selected from kerosene, diesel oil, 200# solvent and raffinate oil in one or more.
9. the application of quench oil viscosity reductant as claimed in claim 1 in control chilling oil viscosity.
10. application as claimed in claim 9 is characterized in that: the interpolation concentration of described quench oil viscosity reductant is the 5-100ppm of quenching oil internal circulating load.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910248005A CN101838522A (en) | 2009-12-31 | 2009-12-31 | Quenching oil viscosity depressant and use thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910248005A CN101838522A (en) | 2009-12-31 | 2009-12-31 | Quenching oil viscosity depressant and use thereof |
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| CN101838522A true CN101838522A (en) | 2010-09-22 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2768791A4 (en) * | 2011-10-19 | 2015-07-15 | Nalco Co | Circulation aid for primary fractional quench loops |
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2009
- 2009-12-31 CN CN200910248005A patent/CN101838522A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2768791A4 (en) * | 2011-10-19 | 2015-07-15 | Nalco Co | Circulation aid for primary fractional quench loops |
| US9505988B2 (en) | 2011-10-19 | 2016-11-29 | Nalco Company | Circulation aid for primary fractional quench loops |
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Application publication date: 20100922 |