CN101062880A - Ethylene device quench oil viscosity reductant - Google Patents
Ethylene device quench oil viscosity reductant Download PDFInfo
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- CN101062880A CN101062880A CN 200610078653 CN200610078653A CN101062880A CN 101062880 A CN101062880 A CN 101062880A CN 200610078653 CN200610078653 CN 200610078653 CN 200610078653 A CN200610078653 A CN 200610078653A CN 101062880 A CN101062880 A CN 101062880A
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Abstract
The invention discloses an ethylene device quench oil viscosity reductant in inhibiting liquid viscosity intensification technical domain, which is characterized by the following: comprising with inhibitor, disperser and metal deactivator; possessing the function of aggregation inhibition, aggregation prevention and metallic surface deactivation; decreasing erosion and incrustation of quench system device; possessing little adding quantity and good stability; non-generating side effect of oil water emulsion.
Description
Technical field
The present invention relates to a kind of viscosity depressant that liquid viscosity increases that suppresses, more particularly, the present invention relates to a kind of viscosity depressant that is used for petrochemical industry ethylene unit quench oil system.
Background technology
Quench oil system is an important component part of ethylene unit, and it directly connects cracking and compression two big units, and its operation quality has material impact to the ethylene unit performance.Quenching oil is the tower still heavy constituent of splitting gas after quenching oil column cooling fractionation, and the boiling range scope is rich in a large amount of easily compounds such as polymeric unsaturated aromatic hydrocarbon, styrenic, indenes class about 220 ℃～500 ℃.The feature of quenching oil self maximum is exactly the prolongation along with the residence time in system, unsaturated component polymerization and saturated component, aromatised fraction condensation are colloid and bituminous matter, has caused quenching oil viscosity to increase with the prolongation of the residence time.And the growth of quenching oil viscosity can cause the reduction of the heat transfer efficiency of quenching oil pump operating cycle efficient and dilution steam generation producer, influences the fractionating effect of gasoline splitter, causes plant energy consumption increase etc.
Traditional quenching oil process for reducing viscosity is that the Pyrolysis gas oil PGO from the extraction of gasoline splitter side line directly is injected into gasoline splitter tower still by pump.Pyrolysis gas oil PGO is injected in the quenching oil, can play the effect that reduces viscosity, but because the capacity of quenching oil is very big, in order to reduce viscosity, needs a large amount of Pyrolysis gas oil PGOs usually, and needs long-time the injection.Mixing Pyrolysis gas oil PGO can increase its internal circulating load in gasoline splitter, strengthens gasoline splitter middle part gas phase load, correspondingly reduces the processing power of gasoline splitter, and this is disadvantageous for script gasoline splitter limited in one's ability.Therefore, this is a kind of makeshift, can't fundamentally solve the problem that quenching oil viscosity raises.
Along with the variation of ethylene unit cracking stock and being extensive use of of heavy cracking stock, quenching oil viscosity controller technology has obtained developing rapidly.World's ethylene unit newly-built and enlarging has mostly adopted the visbreaking tower technology at present.The visbreaking tower quenching oil fractionate out selectively gently, heavy constituent, light constituent returns gasoline splitter, heavy constituent are as the Pyrolysis fuel oil PFO extraction, reach the purpose that reduces quenching oil viscosity with this.But visbreaking tower operating parameters is difficult to control, and domestic a lot of visbreaking towers are inactive.
The use of viscosity depressant generally comes into one's own both at home and abroad at present.Be representative abroad, suppress quenching oil viscosity, obtained effect preferably on the device abroad by adding quench oil viscosity reductant with Nalco company.But owing to the difference of processing condition, expensive reasons such as price are used on the ethylene unit seldom at home.
Along with the development of ethylene production, viscosity depressant also will have good dispersion, metal passivation and corrosion resistance except the antioxygen polymerization inhibition performance will be arranged, and this just need develop viscosity depressant efficiently.
US6096188 discloses in quenching oil and to have added age-inhibiting addition and control the quenching oil method of viscosity, and this method control tower still simultaneously is stable.Additive can be the mixture of one or several materials in alkylphenol, alkyl diphenol, alkyl connection phenol, arylamine, the nitro oxide.Yet this additive does not have and disperses and the metal passivation function, and the visbreaking effect is also not obvious.
US5985940 has described by add (single or poly-) alkylbenzene phenol-formaldehyde resin in quenching oil and has stablized quench oil system, realizes the method for scale inhibition, visbreaking and decoking.This resin makes under the acid catalysis effect, and molecular weight is 1000～30000, and alkyl substituent has 9～16 carbon atoms at least, can be side chain or straight chain.As: poly-nonyl phenol-dinonyl phenol-formaldehyde resin, molecular weight is 2000～10000.Yet this viscosity depressant generates by polymerization, the bad control of molecular weight, and do not possess dispersion and metal passivation function.
US5824829 points out that the growth of quenching oil viscosity is owing to the polymerization at high temperature of undersaturated aromatic component causes.By adding the mixture of one or more materials in alkyl benzene sulphonate (ABS) (salt) and arylamine, phenols, hydroquinones, the dialkyl group azanol class, reach the purpose that reduces quenching oil viscosity.Wherein the alkyl in the alkyl benzene sulphonate (ABS) (salt) can be the straight or branched that contains 4～32 carbon atoms; Salt can be primary amine salt, secondary amine salt, tertiary ammonium salt etc., and wherein the amine salt carbon atom quantity is 1～22 alkyl straight-chain or side chain, and on the chain hydroxyl or alkoxyl group can be arranged.This viscosity depressant does not contain dispersion agent, and the carbon distribution, the gelatinoid that are difficult to will form effectively disperse.
CN1566042A has proposed the quench oil viscosity reductant in a kind of cracking fractionator, and is formulated by dispersion agent and stopper, and the part by weight of dispersion agent and stopper is 1: 0.1～10.Wherein dispersion agent is to be two succimides of 1000～3000 polyisobutene preparation by molecular weight, and stopper is formulated by Hinered phenols antioxidant and phosphite ester kind antioxidant, and both part by weight are 1: 0.1～8.At the bottom of quenching oil column, add viscosity depressant 100～5000ppm and just can effectively control the growth of chilling oil viscosity, and can not cause the emulsification of quenched water in the system, the fouling that can slow down equipment in the quenching system simultaneously.But this viscosity depressant add-on is excessive, system is not exerted an influence unavoidably, and this viscosity depressant containing metal passivator not, and industrial use can have problems.
In sum, it is undesirable that existing quench oil viscosity reductant exists the visbreaking effect, and can not have both simultaneously and disperse and the performance of passive metal, press for exploitation a kind of can be simultaneously the efficient quench oil viscosity reductant of visbreaking, dispersion and passive metal.
Summary of the invention
The present invention is undesirable and lack the problem of disperseing with passive metal for the visbreaking effect that solves existing quench oil viscosity reductant and exist, and has proposed a kind of new and effective quench oil viscosity reductant, and this viscosity depressant is made up of stopper, dispersion agent and metal passivator.By adding this new and effective viscosity depressant in the quenching oil under different technology conditions, can control the growth of quench oil system viscosity, thereby the heat transfer efficiency of quenching oil pump operating cycle efficient and dilution steam generation producer is improved, and the separating effect of gasoline splitter improves, and plant energy consumption reduces.
Concrete technical scheme is as follows.
Ethylene device quench oil viscosity reductant of the present invention comprises stopper, dispersion agent and metal passivator.
The weight ratio of described stopper, dispersion agent and metal passivator can be carried out suitable adjusting by needs according to circumstances, for example in the system of easy polymerization reaction take place, the ratio of stopper can be suitably improved, in the more system of jelly, the ratio of dispersion agent can be suitably improved.In quench oil viscosity reductant of the present invention, the weight ratio of described stopper, dispersion agent and metal passivator is preferably 1～10: 1: 0.1～3.The weight ratio of described stopper, dispersion agent and metal passivator more preferably 3: 1: 1.
Stopper can stop the carrying out of radical chain reaction, and polyreaction is stopped, thus the increase of containment viscosity.Stopper used in the present invention is an oxidation inhibitor.Described stopper preferably is made up of phenolic antioxidant and amine antioxidants, and the weight ratio of described phenolic antioxidant and amine antioxidants is preferably 1: 0.2～and 5, more preferably 1: 1.
Described phenolic antioxidant has 2 for example, 6-di-tert-butyl-4-methy phenol, 2,4-di-t-butyl-6-methylphenol, 2,6-dimethyl-4-ethylphenol, 2, the mixture of one or more in 4-dimethyl-6-ethylphenol and the Resorcinol, described amine antioxidants has 2-ethyl oxyamine, 2-propyl hydroxy amine, N for example, N '-di-t-butyl Ursol D, N, the mixture of one or more in N '-biphenyl Ursol D, N-(1-iso-octyl) Ursol D.
The preparation method of described stopper is simple mixing, and is just that phenolic antioxidant and amine antioxidants is even according to suitable mixed, for example stirs in container.
Dispersion agent is the mutual accumulation of barrier carbon distribution and jelly effectively, by charge repulsion peptization macroparticle more, makes it to be scattered in the oil.The dispersion agent that the present invention uses is preferably one or more the mixture in polymerase chain alkenyl succinimide and the polymerase chain alkenyl succinimide phosphorous derivant, for example polyisobutenyl succinimide and with the product of tolytriazole and aldehyde reaction, the phosphorous derivant that polyisobutenyl succinimide and formaldehyde and phosphatase reaction make.
Have H owing to enter the material of quenching oil column
2S, CO
2, sour gas such as organosulfur, increased corrosive nature to equipment.This corrosive metal-salt very easily is sticked together with high molecular polymer, on tower wall, tower tray and tower still.Therefore a kind of good viscosity depressant also should consider to have the metal passivation effect.Metal passivator is adsorbed on the metallic surface, forms protective membrane, can prevent that metal from further corroding, and takes place thereby reduce polymeric.
The metal passivator that the present invention uses is preferably one or more the mixture in poly-alkylsiloxane, benzene sulfonamide amine acid salt and the alkyl naphthalene sulfonic acid amine salt.For example: polymethyl siloxane, to tert.-butylbenzene (naphthalene) sulfonic acid and amine salt, tert.-amylbenzene (naphthalene) sulfonic acid and amine salt thereof, dodecylbenzene (naphthalene) sulfonic acid and amine salt thereof etc.
The preparation method of quench oil viscosity reductant of the present invention is simple blending means, for example in container stopper, dispersion agent and metal passivator is mixed according to predetermined ratio.
The using method of viscosity depressant of the present invention is simple, be added in the quenching system just passable, general add-on is 10～1000ppm (weight), and viscosity depressant of the present invention can not cause the emulsification of quenched water in the system, the fouling that can slow down equipment in the ethylene unit quenching system simultaneously.
Viscosity depressant of the present invention has following characteristics:
(1) viscosity depressant of the present invention is to form by stopper, dispersion agent and metal passivator are composite.Wherein, stopper can stop the carrying out of radical chain reaction, and dispersion agent is the mutual accumulation of barrier carbon distribution and jelly effectively, and metal passivator can form protective membrane in the metallic surface, can control the increase of quenching oil viscosity effectively.
(2) viscosity depressant of the present invention can slow down the equipment corrosion of quench oil system, reduces the fouling of equipment in the quench oil system, thereby improves the operational efficiency of quenching oil recycle pump and the heat transfer efficiency of dilution steam generation producer, improves the fractionating effect of quenching oil column;
(3) add-on of viscosity depressant of the present invention is very little, can not cause the emulsification of quenched water in the system, and system operation is had no adverse effects.
Description of drawings
Fig. 1 is embodiment 1 and 2 and the figure of the visbreaking effect that obtains of Comparative Examples 1 and 2.
Embodiment
Further explain the present invention in the mode of embodiment below, but the present invention is not limited to these embodiment.
Embodiment 1
Phenolic antioxidant is selected 2,6 ditertiary butyl p cresol, and amine antioxidants is selected 2-ethyl oxyamine, is that 4: 3 mixed is mixed with stopper by weight with phenolic antioxidant and amine antioxidants.
Dispersion agent selection molecular weight is 2,000 polyisobutenyl succinimide.
Metal passivator selection molecular weight is 1,500 poly-methyl siloxanes.
Above-mentioned stopper, dispersion agent and metal passivator were mixed the quench oil viscosity reductant of preparation cost embodiment by weight 3: 1: 1.
Under 200 ℃ temperature, 1000 gram quenching oil samples (taking from the quenching system of Yanshan Mountain ethylene unit) are joined in the airtight metal device, the viscosity depressant that adds present embodiment, add-on is 500ppm (weight), constant temperature 48 hours, get one time sample in per 4 hours, measure the kinematic viscosity of quenching oil sample.Test-results as shown in Figure 1.As can be seen from Figure 1, under given test conditions, the chilling oil viscosity that adds the viscosity depressant of present embodiment increasess slowly, and shows that viscosity depressant of the present invention has more significant visbreaking effect.
Embodiment 2
Phenolic antioxidant selects 2,6-dimethyl-4-ethylphenol, and amine antioxidants is selected N, and N '-di-t-butyl Ursol D is that 1: 1 mixed is mixed with stopper with phenolic antioxidant and amine antioxidants by weight.
Dispersion agent selection molecular weight is 2,000 polyisobutenyl succinimide.
Metal passivator is selected Witco 1298 Soft Acid.
Above-mentioned stopper, dispersion agent and metal passivator were mixed the quench oil viscosity reductant of preparation cost embodiment by weight 3: 1: 1.
Under 200 ℃ temperature, 1000 gram quenching oil samples (identical with embodiment 1) are joined in the airtight metal device, do not add any viscosity depressant, constant temperature 48 hours was got sample one time in per 4 hours, measured the kinematic viscosity of quenching oil sample.Test-results as shown in Figure 1.
Comparative Examples 1
This Comparative Examples is blank simultaneous test.
Under 200 ℃ temperature, 1000 gram quenching oil samples (identical with embodiment 1) are joined in the airtight metal device, do not add any viscosity depressant, constant temperature 48 hours was got sample one time in per 4 hours, measured the kinematic viscosity of quenching oil sample.Test-results as shown in Figure 1.
Comparative Examples 2
Under 200 ℃ temperature, 1000 gram quenching oil samples (identical with embodiment 1) are joined in the airtight metal device, add the HK-1818 viscosity depressant that commercially available Chemical Engineering Institute, HangZhou City company limited produces, add-on is 500ppm (weight), constant temperature 48 hours, get one time sample in per 4 hours, measure the kinematic viscosity of quenching oil sample.Test-results as shown in Figure 1.
Embodiment 3
Present embodiment is a thermostability of measuring quench oil viscosity reductant of the present invention.
The service temperature of quench oil circulated generally is controlled at below 220 ℃, but can directly contact with the Pintsch process gas from pyrolyzer in system, and decomposition in various degree all can take place general chemical.If viscosity depressant through once circulation, whole or most of the decomposition, then can lose the visbreaking effect with quenching oil.The decomposition temperature that adopts DSC method (Differential Scanning Calorimetry, differential scanning calorimeter) to measure viscosity depressant of the present invention is 350 ℃.So the possibility that this viscosity depressant decomposes under quenching system is very little, can not influence its visbreaking effect.
Embodiment 4
Present embodiment is an oil-water emulsion phenomenon of measuring quench oil viscosity reductant of the present invention.
In quenching system, in quenching oil, add viscosity depressant and tend to produce the oil-water emulsion phenomenon.Therefore viscosity depressant will arouse attention to the influence, the particularly influence to oil-water emulsion of quenching system, otherwise brings difficulty can for the separation of post-order process.
In the 150ml graduated cylinder, add 50ml pyrolysis gasoline and 50ml water, in pyrolysis gasoline, drip the quench oil viscosity reductant of the embodiment 1 of 1000ppm (weight), graduated cylinder is put into the water bath with thermostatic control of 81 ℃ (service temperatures of quenching system oily water separation) and heated 20 minutes.Used electronic stirring rake vigorous stirring 10 minutes, the record water-oil interface.Test-results sees Table 1.
Table 1 oil-water emulsion experimental result
| Before viscosity depressant adds | After viscosity depressant adds | |
| Oil reservoir (cm) | 50, transparent | 50, transparent |
| Water layer (cm) | 50, transparent | 50, transparent |
| The oily water separation time (second) | 20 | 20 |
| Emulsion layer (cm) | 0 | 0 |
| State of interface | The interface is clear | The interface is clear |
As can be seen from Table 1, add viscosity depressant of the present invention to the oil-water emulsion of quenching system without any influence.
Claims (8)
1. an ethylene device quench oil viscosity reductant is characterized in that, described viscosity depressant comprises stopper, dispersion agent and metal passivator.
2. quench oil viscosity reductant as claimed in claim 1 is characterized in that, the weight ratio of described stopper, dispersion agent and metal passivator is 0.1～10: 1: 0.1～10.
3. quench oil viscosity reductant as claimed in claim 2 is characterized in that, the weight ratio of described stopper, dispersion agent and metal passivator is 3: 1: 1.
4. as each described quench oil viscosity reductant in the claim 1～3, it is characterized in that described stopper is made up of phenolic antioxidant and amine antioxidants, the weight ratio of described phenolic antioxidant and amine antioxidants is 1: 0.2～5.
5. quench oil viscosity reductant as claimed in claim 4 is characterized in that, the weight ratio of described phenolic antioxidant and amine antioxidants is 1: 1.
6. quench oil viscosity reductant as claimed in claim 4, it is characterized in that, described phenolic antioxidant is 2,6-di-tert-butyl-4-methy phenol, 2,4-di-t-butyl-6-methylphenol, 2,6-dimethyl-4-ethylphenol, 2, the mixture of one or more in 4-dimethyl-6-ethylphenol and the Resorcinol, described amine antioxidants is 2-ethyl oxyamine, 2-propyl hydroxy amine, N, N '-di-t-butyl Ursol D, N, the mixture of one or more in N '-biphenyl Ursol D, N-(1-iso-octyl) Ursol D.
7. as each described quench oil viscosity reductant in the claim 1～3, it is characterized in that described dispersion agent is one or more the mixture in polymerase chain alkenyl succinimide and the polymerase chain alkenyl succinimide phosphorous derivant.
8. as each described quench oil viscosity reductant in the claim 1～3, it is characterized in that described metal passivator is one or more the mixture in poly-alkylsiloxane, benzene sulfonamide amine acid salt and the alkyl naphthalene sulfonic acid amine salt.
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| CN 200610078653 CN101062880A (en) | 2006-04-29 | 2006-04-29 | Ethylene device quench oil viscosity reductant |
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| CN 200610078653 CN101062880A (en) | 2006-04-29 | 2006-04-29 | Ethylene device quench oil viscosity reductant |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102070394A (en) * | 2010-12-22 | 2011-05-25 | 浙江杭化科技有限公司 | Scale inhibitor for styrene rectification system |
| 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 |
| CN103827064A (en) * | 2011-10-19 | 2014-05-28 | 纳尔科公司 | Circulation aid for primary fractional quench loops |
| CN110437025A (en) * | 2019-06-26 | 2019-11-12 | 通用电气神华气化技术有限公司 | A kind of olefin separation spent lye visbreaking polymerization inhibitor agent prescription |
-
2006
- 2006-04-29 CN CN 200610078653 patent/CN101062880A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN102070394A (en) * | 2010-12-22 | 2011-05-25 | 浙江杭化科技有限公司 | Scale inhibitor for styrene rectification system |
| CN103827064A (en) * | 2011-10-19 | 2014-05-28 | 纳尔科公司 | Circulation aid for primary fractional quench loops |
| 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 |
| CN103827064B (en) * | 2011-10-19 | 2017-04-26 | 纳尔科公司 | Circulation aid for primary fractional quench loops |
| CN110437025A (en) * | 2019-06-26 | 2019-11-12 | 通用电气神华气化技术有限公司 | A kind of olefin separation spent lye visbreaking polymerization inhibitor agent prescription |
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