CN103768832B - A kind of delayed coking antifoaming agent composition and method of making the same - Google Patents
A kind of delayed coking antifoaming agent composition and method of making the same Download PDFInfo
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- CN103768832B CN103768832B CN201210408462.8A CN201210408462A CN103768832B CN 103768832 B CN103768832 B CN 103768832B CN 201210408462 A CN201210408462 A CN 201210408462A CN 103768832 B CN103768832 B CN 103768832B
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Abstract
The present invention relates to a kind of delayed coking antifoaming agent composition and method of making the same, this defoamer is composited by fluorinated polysiloxane, glycerol type dendritic polyether, high-carbon alcohol and solvent.Fluorinated polysiloxane is scattered in higher alcohols by defoamer preparation method of the present invention, stirs 1 ~ 2 hour, then add glycerol type dendritic polyether and solvent at 10 ~ 30 DEG C, 100 ~ 150 DEG C of stirring reactions 1 ~ 5 hour, obtains anti-foam product after cooling.Delayed coking antifoaming agent of the present invention, has good antifoaming performance at 400 ~ 500 DEG C; In the delayed coking of high temperature, still good antifoaming performance and stability can be kept.
Description
Technical field
The present invention relates to a kind of defoaming agent composition and preparation method thereof, particularly relate to a kind of defoaming agent composition introducing fluorinated polysiloxane and glycerol type dendritic polyether, belong to technical field of fine, defoamer of the present invention is particularly useful for delayed coking field.
Background technology
Delayed coking is a kind of heat processing technique residual oil drastic cracking being converted into coking dry gas, coking gasoline and diesel, wax tailings and coke.Containing natural surfactant in the feed residue of delayed coking, make in delayed coking, produce a large amount of foam in pyrogenetic reaction tower, form very high froth bed.Containing a large amount of coke powder in froth bed, when in coking later stage coke drum, focus layer rises to certain altitude, froth bed is carried to fractionating column with coking oil gas from the oil-gas pipeline of top of coke tower, cause fractionating column coking, and then cause Fractionator Bottom recursive filter, radiant section charge filter and feed pump to block, tube coking, affects the safety in production of device.The coke powder be carried in fractionating column is carried secretly through fractionating device part to be entered in coker gasoline, diesel oil, works the mischief to follow-up hydrogenation technique.
In order to eliminate the adverse effect of foam layer in coke tower, current universal method adopts to use defoamer to carry out froth breaking at coke drum, and after defoamer is used for froth bed, sprawl rapidly at liquid surface, bioactive molecule wherein makes bubble burst speed accelerate.The defoamer of early application is the dimethicone that silicone content is higher, uses this high silicon defoaming agent, although can froth breaking fast, coker gasoline, diesel oil can be made to produce silicon and pollute, cause downstream hydrogenation device catalyst poisoning.The defoamer of current use belongs to low silicon organic silicon type substantially.
US3700587 discloses a kind of defoamer for eliminating foam in coke drum, and its main component is dimethyl silicone polymer, and after adding 0.5 ~ 100ppm defoamer, tower inner foam layer highly significant reduces.But the silicone content of this defoamer is high, element silicon can be deposited on delayed coking unit later stage Hydrobon catalyst, causes catalyst poisoning inactivation, shortens catalyst regeneration time swap interval, reduces production efficiency.
CN101444708A discloses a kind of defoamer of low silicon content, is composited primarily of froth breaking component organosiloxane and hydrophobic silica, suds suppressing component organosilicon modified polyether and long-chain fatty alcohol, solvent hydrogenated diesel oil, kerosene and heavy aromatics etc.It is low that this kind of defoamer has silicone content, and froth breaking presses down the advantages such as bubble ability is strong, but due to constantly accumulative on delayed coking unit later stage hydrogenation catalyst of element silicon, still inevitably cause catalyst poisoning inactivation, reduce production efficiency.
CN101045880 discloses a kind of defoamer be composited by polymer blocks polyethers, fatty alcohol and solvent, its polymer blocks polyethers to be molecular weight be 10000 ~ 20000 polyethylene glycol, for the block copolymer of initiator oxirane and expoxy propane, fatty alcohol is isooctanol, and solvent is second alcohol and water.Not containing any element silicon in this defoamer, can not impact downstream hydrogenation process and final clean or white quality, but it is inadequate that shortcoming is active component, in tower, infiltration and diffusion are slowly, therefore cause addition large, cost is higher than silicone defoaming agent, and resistance to elevated temperatures is poor simultaneously, and under high temperature, defoaming effectiveness is low.
US5667669 provides a kind of method that animal and vegetable oil and polyisobutene etc. replace containing silicon defoaming agent, froth breaking cost not only can be made to increase, and defoaming effect is general.
Summary of the invention
For the deficiencies in the prior art, the invention provides that a kind of defoaming effectiveness is high, high temperature resistant, compound low silicon defoaming agent that stable performance, good dispersion, antifoaming speed are fast and preparation method thereof.
Defoaming agent composition of the present invention, comprises in mass fraction:
Fluorinated polysiloxane 1-30 part;
Glycerol type dendritic polyether 1-20 part;
Higher alcohols 10-40 part;
Balance of solvent.
In defoaming agent composition of the present invention, described fluorinated polysiloxane polysiloxanes side chain is introduced fluoroalkyl to carry out the product that modification obtains, and owing to introducing the difference of fluoroalkyl chain length, has the fluorinated polysiloxane of different structure.The preferred trifluompropyl methyl polysiloxane of the present invention, viscosity is 2000 ~ 100000cst.Trifluompropyl methyl polysiloxane can use the commercial product meeting index request, or by existing method preparation, as first obtained trifluoropropylmethyldichlorosilane by trifluoro propene and dichloromethylsilane generation hydrosilylation, then through obtained three ring bodies 2 of the steps such as hydrolysis, cracking, 4,6-trimethyl-2,4,6-tri-(3 ', 3 ', 3 '-trifluoro propyl) cyclotrisiloxane, then under the effect of base catalyst, there is ring-opening polymerization, obtain product trifluompropyl methyl polysiloxane.
In defoaming agent composition of the present invention, described glycerol type dendritic polyether can use the commercial product meeting index request, or by existing method preparation, as started with trimethylolethane by divergent method, through 3 allylations repeatedly and hydroxylation, can obtain the glycerol type dendritic polyether of three generations, its surface is with 24 functional groups.
In defoaming agent composition of the present invention, described higher alcohols are the alcohol of C7 ~ C9, and the alcohol of C7 ~ C9 has 3-enanthol, isooctanol or 2-Ethylhexyl Alcohol.
In defoaming agent composition of the present invention, described solvent is hydrogenated diesel oil, kerosene, fuel oil, wax tailings or machine oil, preferred kerosene or hydrogenated diesel oil.
In defoaming agent composition of the present invention, optionally can also add one or more in fatty alcohol, non-ionic surface active agent, polyisobutene compound, sulfonate and phosphate compounds, animal oil, plant wet goods, consumption is 1 ~ 20 mass parts.
The preparation method of defoaming agent composition of the present invention is: be scattered in by fluorinated polysiloxane in higher alcohols, stir 1 ~ 2 hour at 10 ~ 30 DEG C, then add glycerol type dendritic polyether and solvent, at 100 ~ 150 DEG C, stirring reaction 1 ~ 5 hour, obtains anti-foam product after cooling.
The application of defoaming agent composition of the present invention in delay coking process.When delayed coking foam layer in coke tower is higher, add defoaming agent composition of the present invention at tower top, or defoaming agent composition of the present invention uses jointly with other defoamer, carries out defoaming treatment to delayed coking coke drum.Consumption is generally 10 ~ 100 μ g/g, is preferably 30 ~ 80 μ g/g.
Compared with prior art, the fluorinated polysiloxane introduced in defoamer of the present invention, because its side chain is the CF with minimum surface energy
3and CF
2group, thus show as lower surface tension, higher chemical inertness, stronger defoaming capacity.Compared with common polysiloxanes, need the fluorinated polysiloxane of small amount, just can realize identical foam and control, thus reduce the addition of defoamer; The glycerol type dendritic polyether structure height used is regular, with other Suitable ingredients with the use of time, strand is easy entanglement not, good with materials compatibility in tower, and spreading coefficient is large, and in tower, diffusion is fast, and antifoaming speed is fast, presses down bubble effect lasting.Therefore defoaming agent composition of the present invention uses in coking, not only at high temperature there is good froth breaking and press down bubble ability, and compared with common polysiloxane defoamers, reduce the addition of defoamer, thus significantly reduce the silicone content in coke chemicals.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described further, but the present invention is not limited to these embodiments.
Embodiment 1
Be that 30000 ~ 40000cst fluorinated polysiloxane is scattered in the 2-Ethylhexyl Alcohol of 20 parts by 10 parts of viscosity, stir 1 hour in the waters of 20 DEG C, then add 10 parts of glycerol type dendritic polyethers and 60 parts of hydrogenated diesel oils, at 130 DEG C, stirring reaction 3 hours, obtains anti-foam product after cooling.
Embodiment 2
Be that 40000 ~ 50000cst fluorinated polysiloxane is scattered in the 3-enanthol of 30 parts by 5 parts of viscosity, stir 1 hour in the waters of 30 DEG C, then add 10 parts of glycerol type dendritic polyethers and 55 parts of kerosene, at 130 DEG C, stirring reaction 3 hours, obtains anti-foam product after cooling.
Embodiment 3
Be that 30000 ~ 40000cst fluorinated polysiloxane is scattered in the 3-enanthol of 30 parts by 10 parts of viscosity, stir 1 hour in the waters of 20 DEG C, then add 5 parts of glycerol type dendritic polyethers and 55 parts of kerosene, at 120 DEG C, stirring reaction 4 hours, obtains anti-foam product after cooling.
Embodiment 4
Be that 40000 ~ 50000cst fluorinated polysiloxane is scattered in the isooctanol of 30 parts by 5 parts of viscosity, stir 1 hour in the waters of 20 DEG C, then add 5 parts of glycerol type dendritic polyethers and 60 parts of wax tailings, at 130 DEG C, stirring reaction 3 hours, obtains anti-foam product after cooling.
Embodiment 5
Be that 40000 ~ 50000cst fluorinated polysiloxane is scattered in the 2-Ethylhexyl Alcohol of 35 parts by 5 parts of viscosity, stir 1 hour in the waters of 20 DEG C, then add 5 parts of glycerol type dendritic polyethers and 55 parts of hydrogenated diesel oils, at 120 DEG C, stirring reaction 2 hours, obtains anti-foam product after cooling.
Evaluate the antifoam performance of defoamer of the present invention below by experimental data, comparative example is defoamer prepared by commercially available common dimethyl silicone polymer.
200mL expanding foam solution (coker gasoline: coking light distillate: coking heavy distillate=500:1250:1000 (wt%)) is added in 1000mL graduated cylinder, with plug by graduated cylinder lid, insert in expanding foam solution by thermocouple, liquid to be foamed stablizes 10min after being warming up to 400 DEG C simultaneously.Open intake valve, in expanding foam solution, pass into nitrogen by gas diffusion tip.After froth bed is stable, namely STATIC FOAM is after a certain height continues not change for one minute, and record froth bed maximum height, is designated as H
0, unit mm.Add defoamer solution on foam top simultaneously fast, record froth bed minimum altitude, is designated as H
1, unit mm.Wherein defoamed ratio (ε) computing formula is: ε=(H
0-H
1) × 100%/H
0, wherein H
0for the froth bed maximum height before adding defoamer, mm; H
1for adding the froth bed minimum altitude after defoamer, mm.
Defoamed ratio (%) under the different addition of table 1
| Defoamer consumption | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Comparative example |
| 20μg/g | 91.1 | 86.5 | 90.2 | 86.3 | 89.1 | 72.1 |
| 50μg/g | 92.2 | 91.7 | 91.5 | 90.7 | 91.7 | 81.7 |
| 100μg/g | 93.4 | 92.3 | 92.6 | 92.6 | 92.3 | 91.6 |
From table 1, data analysis can draw, defoamer prepared by the embodiment of the present invention 1 ~ 5 is under the addition of 20 μ g/g, defoamed ratio is all greater than 86%, wherein embodiment 1, embodiment 3 are more than 90%, and the defoamed ratio of defoamer under equal addition prepared by common dimethyl silicone polymer is only 72.1%, well below the defoamed ratio of the embodiment of the present invention 1 ~ 5 gained defoamer.There is the fluorinated polysiloxane of more low surface tension due to used in the present invention and there is better extensibility and press down the lasting glycerol type dendritic polyether of bubble ability, can well be scattered in again in high-carbon alcohol and solvent simultaneously, make it spread fast at foam surface, therefore the defoamer of less consumption just can reach good defoaming effect.
Claims (9)
1. a defoaming agent composition, is characterized in that amounting to 100 parts with fluorinated polysiloxane, glycerol type dendritic polyether, higher alcohols, solvent quality number, comprising:
Fluorinated polysiloxane 1-30 part;
Glycerol type dendritic polyether 1-20 part;
Higher alcohols 10-40 part;
Balance of solvent;
Wherein, described fluorinated polysiloxane is trifluompropyl methyl polysiloxane, viscosity is 2000 ~ 100000cst, described glycerol type dendritic polyether is started with trimethylolethane by divergent method, through 3 allylations repeatedly and hydroxylation, the three generations's glycerol type dendritic polyether obtained.
2. according to defoaming agent composition according to claim 1, it is characterized in that: described higher alcohols are the alcohol of C7 ~ C9.
3. according to the defoaming agent composition described in claim 1 or 2, it is characterized in that: described higher alcohols are 3-enanthol, isooctanol or 2-Ethylhexyl Alcohol.
4. according to defoaming agent composition according to claim 1, it is characterized in that: described solvent is kerosene, hydrogenated diesel oil, fuel oil, wax tailings or machine oil.
5. according to the defoaming agent composition described in claim 1 or 4, it is characterized in that: described solvent is kerosene or hydrogenated diesel oil.
6. according to defoaming agent composition according to claim 1, it is characterized in that: in described defoaming agent composition, also comprise one or more in fatty alcohol, non-ionic surface active agent, polyisobutene compound, sulfonate and phosphate compounds, animal oil, vegetable oil, mass fraction is 1 ~ 20 part.
7. the preparation method of arbitrary described defoaming agent composition in claim 1 ~ 6, comprise: fluorinated polysiloxane is scattered in higher alcohols, stir 1 ~ 2 hour at 10 ~ 30 DEG C, then glycerol type dendritic polyether and solvent is added, at 100 ~ 150 DEG C, stirring reaction 1 ~ 5 hour, obtains anti-foam product after cooling.
8. the application of the defoaming agent composition in claim 1 ~ 6 described in arbitrary claim in delay coking process.
9. according to application according to claim 8, it is levied and is: the consumption of defoaming agent composition is 10 ~ 100 μ g/g.
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Families Citing this family (6)
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| CN104436763B (en) * | 2014-11-14 | 2017-10-31 | 衢州氟硅技术研究院 | A kind of fluorosilicone antifoam and preparation method thereof |
| CN106693453A (en) * | 2016-12-28 | 2017-05-24 | 广东中联邦精细化工有限公司 | Defoaming agent for producing industrial detergent and preparation method of defoaming agent |
| CN107540387A (en) * | 2017-08-31 | 2018-01-05 | 安徽省德邦瓷业有限公司 | A kind of porcelain sintering defoamer being built in kiln |
| CN107737467B (en) * | 2017-10-23 | 2019-12-13 | 付海明 | Delayed coking defoaming agent and preparation method and application thereof |
| CN109180523B (en) * | 2018-09-12 | 2021-08-27 | 湖南化工研究院有限公司 | Defoaming method of amide compound and phosgene reaction system |
| CN111265916B (en) * | 2020-01-21 | 2022-07-15 | 山东京博石油化工有限公司 | Delayed coking defoaming agent and preparation method and application thereof |
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