CN103768835A - Defoaming agent composition and application in delay coking - Google Patents
Defoaming agent composition and application in delay coking Download PDFInfo
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- CN103768835A CN103768835A CN201210408481.0A CN201210408481A CN103768835A CN 103768835 A CN103768835 A CN 103768835A CN 201210408481 A CN201210408481 A CN 201210408481A CN 103768835 A CN103768835 A CN 103768835A
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Abstract
The invention relates to a non-silicon defoaming agent composition which is prepared by compounding 30 to 50 parts by mass of glycerol-type dendritic polyether, 20 to 40 parts by mass of high carbon alcohol fatty acid ester or fatty acid amide and 20 to 30 parts by mass of a solvent. The non-silicon defoaming agent composition does not contain silicon, is good in dispersibility, high in defoaming speed, when the adding amount is about 30 mu g / g, the defoaming rate can reach over 90%, and the non-silicon defoaming agent composition has a strong defoaming performance, and can be used for coke tower defoaming processing in the delay coking process.
Description
Technical field
The present invention relates to a kind of defoaming agent composition and application thereof, particularly relate to a kind of composite silicon-free defoamer composition and the application in delayed coking coke drum thereof, belong to fine chemical technology field.
Background technology
Delayed coking is a kind of heat processing technique that residual oil drastic cracking is converted into coking dry gas, coker gasoline, coker gas oil, wax tailings and coke.In the raw material residual oil of delayed coking, contain natural surfactant, make in delayed coking, in pyrogenetic reaction tower, produce a large amount of foams, form very high froth bed.In froth bed, contain a large amount of coke powders, when in coking later stage coke drum, burnt 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 charging filter and feed pump to stop up, tube coking, affects the safety in production of device.The coke powder being carried in fractionating column is carried secretly and is entered in coker gasoline, diesel oil through fractionating device part, and follow-up hydrogenation technique is worked the mischief.
In order to eliminate the adverse effect of foam layer in coke tower, current universal method is to adopt at coke drum to use defoamer to carry out froth breaking, and defoamer, for after froth bed, is sprawled rapidly at liquid surface, and bioactive molecule is wherein accelerated bubble burst speed.The defoamer of early application is the dimethicone that silicone content is higher, uses this high silicon defoaming agent, although froth breaking fast can make coker gasoline, diesel oil produce silicon and pollute, causes downstream hydrogenation plant catalyst poisoning.The defoamer using at present belongs to low silicon organosilicon type substantially, but still the coke chemicals hydrofining technology in downstream is brought to harm.As silicon can be deposited on catalyst for refining, cause catalysqt deactivation, shorten the running time of device.Therefore, the developing direction of defoamer will be become without silicon product.
US3700587 discloses that a kind of its main component is dimethyl silicone polymer for eliminating the defoamer of coke drum inner foam, adds after 0.5～100ppm defoamer, and tower inner foam layer height significantly 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, has shortened catalyst regeneration time swap interval, has reduced production efficiency.
CN101444708A discloses a kind of defoamer of low silicon content, is mainly composited by 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 the continuous accumulative total of element silicon on delayed coking unit later stage hydrogenation catalyst, still inevitably cause catalyst poisoning inactivation, reduces production efficiency.
CN101045880 discloses a kind of defoamer being composited by macromolecule block polyether, fatty alcohol and solvent, its macromolecule block polyether is that molecular weight is 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.In this defoamer, do not contain any element silicon, can not impact downstream hydrogenation technique and final clean or white quality, but it is inadequate that shortcoming is active component, in tower, infiltration and diffusion are slow, 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.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of efficient delayed coking antifoaming agent without silicon, there is not siliceous, good dispersion, antifoaming speed is fast, defoaming effect is good composite silicon-free defoamer.The present invention also provides the application of a kind of this defoamer in delay coking process.
Defoaming agent composition of the present invention, comprises in mass parts:
Glycerol type dendritic polyether 30-50 part;
Higher alcohols fatty acid ester or fatty acid amide 20-40 part;
Solvent 20-30 part.
In defoaming agent composition of the present invention, described glycerol type dendritic polyether can use the commercial product that meets index request, or by existing method preparation, as started with trimethylolethane by the method for dispersing, through 3 allylation and hydroxylations repeatedly, can obtain three generations's glycerol type dendritic polyether, its surface is with 24 functional groups.
In defoaming agent composition of the present invention, described higher alcohols fatty acid ester is C
8～C
l8saturated fatty acid or unrighted acid and C
8～C
l8the higher alcohols fatty acid ester that condensation obtains under the effect of catalyst, concrete as one or more the preferred octadecanol stearates in Lauryl Alcohol caprylate, ten four carbon alcohols laurates, 16 carbon alcohol oleates, octadecanol stearate etc.; Described fatty acid amide is reacted and obtains at catalyst action with aliphatic acid by amine substance, one or more in concrete as ethylene bis stearamide, the two oleamides of ethylene, ethylenediamine list stearmide or ethylenediamine list oleamide etc., preferred ethylenediamine bis-stearamides.
In defoaming agent composition of the present invention, described solvent is hydrogenated diesel oil, kerosene, fuel oil or wax tailings, preferably wax tailings or hydrogenated diesel oil.
In defoaming agent composition of the present invention, can also optionally 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 mixes required component, stirs and within 0.5～5 hour, obtain defoaming agent composition product at 50～100 ℃.
The application of defoaming agent composition of the present invention in delay coking process.In the time that delayed coking foam layer in coke tower is higher, add defoaming agent composition of the present invention, or defoaming agent composition of the present invention and other defoamer use jointly, delayed coking coke drum is carried out to defoaming treatment.Consumption is generally 10～100 μ g/g, is preferably 20～80 μ g/g.
Compared with prior art, advantage of the present invention is as follows: all components exists without element silicon, and follow-up hydrogenation catalyst and product are had no adverse effects; The glycerol type dendritic polyether structure height using is regular, has a large amount of peripheral hydroxy functional groups, and viscosity is little, dissolubility is good, and unimolecule yardstick is at nanoscale, and molecular shape is spherical, there is fabulous geometrical symmetry, while being used in conjunction with other suitable component, strand is easy entanglement not, good with raw material compatibility in tower, spreading coefficient is large, in tower, soon, antifoaming speed is fast in diffusion, presses down bubble effect lasting; The active constituent of described product all has under good high temperature froth breaking and presses down bubble ability, and active component is many, consumption is little, nontoxic, environmentally safe; All component chemical compositions are stable, particularly more stable under the hot conditions of delayed coking reaction, the effect of sustainable performance froth breaking, to equipment without any corrosion.
The specific embodiment
Below in conjunction with specific embodiment, the present invention is described further, but the present invention is not limited to these embodiment.
Embodiment 1: described defoamer is formulated by the raw material of following mass parts: 30 parts of glycerol type dendritic polyethers, 40 parts of octadecanol stearates, 25 parts of wax tailings, 5 parts of isooctanol.After will above-mentioned raw materials mixing, at 80 ℃, stir 2 hours, make finished product after cooling.
Embodiment 2: described defoamer is formulated by the raw material of following mass parts: 40 parts of glycerol type dendritic polyethers, 15 parts of ethylenediamine bis-stearamides, 15 parts of ethylenediamine list oleamides, 30 parts of wax tailings.Institute stir 2 hours after will above-mentioned raw materials mixing at 100 ℃, make finished product after cooling.
Embodiment 3: described defoamer is formulated by the raw material of following mass parts: 40 parts of glycerol type dendritic polyethers, 20 parts of octadecanol stearates, 15 parts of ethylenediamine bis-stearamides, 25 parts of hydrogenated diesel oils.After will above-mentioned raw materials mixing, at 70 ℃, stir 2 hours, make finished product after cooling.
Embodiment 4: described defoamer is formulated by the raw material of following mass parts: 35 parts of glycerol type dendritic polyethers, 10 parts of ethylene bis stearamides, 10 parts of ethylenediamine list stearmides, ten 15 parts of four carbon alcohols laurates, 30 parts of hydrogenated diesel oils.After will above-mentioned raw materials mixing, at 80 ℃, stir 2 hours, make finished product after cooling.
Embodiment 5: described defoamer is formulated by the raw material of following mass parts: 40 parts of glycerol type dendritic polyethers, 10 parts of Lauryl Alcohol caprylates, 16 10 parts of carbon alcohol oleates, 20 parts of the two oleamides of ethylene, 20 parts of wax tailings.After will above-mentioned raw materials mixing, at 90 ℃, stir 2 hours, make finished product after cooling.
Evaluate the antifoam performance of defoamer of the present invention below by experimental data, comparative example be commercially available certain without silicon delayed coking antifoaming agent.
200mL expanding foam solution (coker gasoline: coking light distillate: coking heavy distillate=500:1250:1000 (mass ratio)) is added in 1000mL graduated cylinder, with plug by graduated cylinder lid, thermocouple is inserted in expanding foam solution simultaneously, be warming up to after 300 ℃ until expanding foam solution, stablize 10min.Open intake valve, ventilate in expanding foam solution by gas diffusion tip.After froth bed is stable, STATIC FOAM, after a certain height continues not change for one minute, records froth bed maximum height, is designated as H
0, the mm of unit.Add defoamer solution on foam top fast, record froth bed minimum altitude, be designated as H simultaneously
1, the mm of unit.Wherein defoamed ratio (ε) computing formula is: ε=(H
0-H
1) × 100%/H
0, wherein H
0for adding defoamer froth bed maximum height before, mm; H
1for adding the froth bed minimum altitude after defoamer, mm.
Defoamed ratio (%) under the different additions of table 1
| Defoamer | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Comparative example |
| 30μg/g | 89.4 | 90.9 | 91.2 | 90.7 | 91.1 | 85.4 |
| 50μg/g | 90.7 | 91.6 | 92.4 | 91.8 | 92.1 | 86.2 |
| 70μg/g | 91.8 | 92.2 | 93.5 | 92.9 | 92.8 | 87.1 |
| 100μg/g | 92.9 | 93.8 | 94.1 | 93.8 | 93.9 | 87.8 |
As can be seen from Table 1, the prepared defoamer of the embodiment of the present invention 1～5 is under the addition of 30 μ g/g, defoamed ratio is all greater than 89%, wherein embodiment 3,5 even exceedes 90%, and commercially available without silicon delayed coking antifoaming agent, the defoamed ratio under equal addition is only 85.4%, well below the defoamed ratio of the embodiment of the present invention 1～5 gained defoamer.Because glycerol type dendritic polyether structure height used in the present invention is regular, there is a large amount of peripheral hydroxy functional groups, viscosity is little, dissolubility is good, and unimolecule yardstick is at nanoscale, has fabulous geometrical symmetry, good with the compound rear compatibility of other components, spreading coefficient is large, and in tower, soon, antifoaming speed is fast in diffusion, therefore its consumption is few, all, between 25～35 μ g/g, by comparison, commercially available need add 100 μ g/g still can not reach close defoamed ratio without silicon delayed coking antifoaming agent.
Claims (10)
1. a defoaming agent composition, is characterized in that comprising in mass parts:
Glycerol type dendritic polyether 20-30 part;
Higher alcohols fatty acid ester or fatty acid amide 20-40 part;
Solvent 20-30 part.
2. according to defoaming agent composition claimed in claim 1, it is characterized in that: described glycerol type dendritic polyether is to start with trimethylolethane by the method for dispersing, through 3 allylation and hydroxylations repeatedly, the three generations's glycerol type dendritic polyether obtaining.
3. according to defoaming agent composition claimed in claim 1, it is characterized in that: described higher alcohols fatty acid ester is C
8～C
l8saturated fatty acid or C
8～C
l8unrighted acid and C
8～C
l8the higher alcohols fatty acid ester that condensation obtains under the effect of catalyst.
4. according to defoaming agent composition claimed in claim 3, it is characterized in that: described higher alcohols fatty acid ester is octadecanol stearate.
5. according to defoaming agent composition claimed in claim 1, it is characterized in that: described fatty acid amide is one or more in the two oleamides of ethylene bis stearamide, ethylene, ethylenediamine list stearmide or ethylenediamine list oleamide.
6. according to defoaming agent composition claimed in claim 5, it is characterized in that: described fatty acid amide is ethylenediamine bis-stearamides.
7. according to defoaming agent composition claimed in claim 1, it is characterized in that: described solvent is hydrogenated diesel oil, kerosene, fuel oil or wax tailings.
8. according to the defoaming agent composition described in arbitrary claim in claim 1 to 7, 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.
9. the application of defoaming agent composition in delay coking process described in the arbitrary claim of claim 1 to 8.
10. according to application claimed in claim 9, it is levied and is: the consumption of defoaming agent composition is 10 μ g/g～100 μ g/g.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105457342A (en) * | 2015-11-24 | 2016-04-06 | 宜兴市丰烨化学有限公司 | Polyether-siloxane glycol antifoaming agent and preparation method thereof |
| CN106807122A (en) * | 2016-12-28 | 2017-06-09 | 广东中联邦精细化工有限公司 | A kind of phosphate fertilizer extraction production defoamer and preparation method thereof |
| CN112717479A (en) * | 2020-12-29 | 2021-04-30 | 新疆水处理工程技术研究中心有限公司 | Polyether defoaming agent and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101045880A (en) * | 2007-04-16 | 2007-10-03 | 沈阳工业大学 | Additive for suppressing and delaying foam generation in coking reaction tower and its prepn process |
| CN101780382A (en) * | 2009-12-07 | 2010-07-21 | 江苏赛欧信越消泡剂有限公司 | Delaying coking non-silicon defoaming agent with multiple active components and preparation method thereof |
-
2012
- 2012-10-24 CN CN201210408481.0A patent/CN103768835B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101045880A (en) * | 2007-04-16 | 2007-10-03 | 沈阳工业大学 | Additive for suppressing and delaying foam generation in coking reaction tower and its prepn process |
| CN101780382A (en) * | 2009-12-07 | 2010-07-21 | 江苏赛欧信越消泡剂有限公司 | Delaying coking non-silicon defoaming agent with multiple active components and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 颉蕊丽: "超支化抗乳化剂的合成及性能研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105457342A (en) * | 2015-11-24 | 2016-04-06 | 宜兴市丰烨化学有限公司 | Polyether-siloxane glycol antifoaming agent and preparation method thereof |
| CN106807122A (en) * | 2016-12-28 | 2017-06-09 | 广东中联邦精细化工有限公司 | A kind of phosphate fertilizer extraction production defoamer and preparation method thereof |
| CN112717479A (en) * | 2020-12-29 | 2021-04-30 | 新疆水处理工程技术研究中心有限公司 | Polyether defoaming agent and preparation method thereof |
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| CN103768835B (en) | 2015-05-13 |
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