CN106467444A - The method that suppression butter generates - Google Patents
The method that suppression butter generates Download PDFInfo
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Abstract
The present invention relates to a kind of method that suppression butter generates, mainly solve that butter inhibition in conventional caustic wash tower is not good, unstable to lead to stifled tower, operate relatively complicated, the technical problem such as relatively costly.The present invention passes through a) to adopt a kind of butter inhibitor (I), in terms of each component parts by weight, including following components：0.5 part～10 parts of aminated compoundss, 0 part～5 parts of alcohol compound；B) inhibitor (I) injects line and alkali liquor (II) via the alkali liquor of caustic wash tower together on-line continuous injects the technical scheme in caustic wash tower (1), solve above-mentioned technical barrier, can be used for suppressing a large amount of generations of butter in the commercial plant caustic wash towers such as oil ethylene, producing ethylene with ethyl alcohol, methanol-to-olefins, vinyl acetate, dichloroethylene, expoxy propane, even cause stifled tower.
Description
Technical field
The present invention relates to a kind of method that suppression butter generates.
Background technology
In low-carbon alkene, ethylene and propylene are important Organic Chemicals, and demand increases year by year.Tradition obtain ethylene, third
The route of alkene is naphtha pyrolysis, and this route relies on oil, and oil has rise in price in a short time, supplies unstable asking
Topic, the problems such as have resource storage capacity limited for a long time.Therefore in recent years as the work being hopeful replacement Petroleum route alkene most
Skill, coal or natural gas obtain via the low-carbon alkene technology such as methanol ethylene, propylene (methanol-to-olefins, MTO or MTP)
Arrive great concern.Either in traditional naphtha pyrolysis route or in emerging methanol-to-olefins technology, it is
Obtain meeting the target product of purity requirement or recycle some unreacted materials, the material flowing out from reactor all need through
Cross a series of isolation of purified process, and be then one of key equipment that material purifies to remove the caustic wash tower of acid impurities.
Caustic wash tower typically with sodium hydrate aqueous solution as medium, when in methanol to olefins reaction generate aldoketoneses impurity through caustic wash tower
When alkaline solution catalysis under easily occur Aldol be condensed, that is, two molecules have α-H aldehydes or ketones condensation generate beta-hydroxy aldehyde,
Then addition forms the clear yellow viscous polymer of certain molecular weight further.Additionally, in course of reaction some diolefins or other
Unsaturated hydrocarbon product also can induce free radical in the presence of trace oxygen, metal ion, and induction is crosslinked to generate polymer,
It is collectively referenced as butter with front described polymer.Butter seriously reduces the alkali cleaning effect of caustic wash tower, consumes a large amount of alkali liquor, and holds
Distributor and filler easily in polymerization fouling blocking tower, cause stifled tower, shorten the cycle of operation of caustic wash tower.And contain a large amount of butter
Salkali waste outside arrange, the operation to downstream processes facility is brought difficulty and produces serious environmental pollution.
The method that the solution a large amount of butter of caustic wash tower generates at present mainly has transformation caustic wash tower, optimizes alkali cleaning operation and interpolation butter suppression
Preparation.Transformation caustic wash tower, optimization alkali cleaning operate and can improve alkali cleaning effect, extension fixture cycle of operation, but can not be fundamentally
Suppression butter generates.Add the generation that butter inhibitor can greatly reduce butter, the butter of generation can also be made simultaneously to divide as early as possible
It is scattered in alkali liquor with alkali liquor discharger, it is to avoid serious environmental pollution, and easy to use, small investment.Patent
US5879534 discloses in dichloroethylene production process, add do not have on α-C the carbonyl compound such as formaldehyde of active H,
Biformyl, benzaldehyde, formic acid, ethanedioic acid, paraformaldehyde, P-methoxybenzal-dehyde etc. are so as to first react to press down with acetaldehyde
System forms polymer.Patent US6986839 discloses butter in one kind amino acidses suppression petroleum installation caustic wash tower
Generation.Patent CN101348410A is by a kind of ternary mixture being made up of alcaminess, hydrazides class, alkyl amine
Carry out butter in ethene suppressing device caustic wash tower.Patent US5264114 discloses one kind aminated compoundss RNH2And R2NH
Carry out the generation of butter in ethene suppressing device caustic wash tower, wherein R is alkyl or aromatic radical.Patent US5900495 discloses
One kind molecular formula is X- (R)n-X1Aminated compoundss suppress propylene oxide unit caustic wash tower in acetaldehyde polymerization, wherein X
Alkylamino radical for amido or containing 1～5 carbon, X1For hydrogen, hydroxyl, amido or the alkylamino radical containing 1～5 carbon；N be 1～
4；R is-CH2NH-, arlydene or the alkyl containing 2～10 carbon.
The butter suppressing method of methanol-to-olefins device caustic wash tower is all not specifically mentioned in above-mentioned patent, and specific aim is not strong,
Inhibitor using effect is not good, unstable, and operation is relatively complicated, relatively costly.
Content of the invention
The technical problem to be solved is in the method that existing suppression butter generates, to methanol-to-olefins device caustic wash tower
Specific aim not strong, inhibitor using effect is not good, unstable, operation relatively complicated, the problems such as relatively costly.The present invention
There is provided the suppressing method that in a kind of methanol-to-olefins device caustic wash tower, butter generates, the method is also not limited to methanol-to-olefins dress
Put caustic wash tower, also can operate with oil ethylene, producing ethylene with ethyl alcohol, preparing propylene from methanol, vinyl acetate, dichloroethylene, epoxy
In the commercial plant caustic wash tower such as propane.
In order to solve above-mentioned technical problem, technical scheme is as follows：A kind of suppression butter generate method, including with
Lower step：
A) adopt a kind of butter inhibitor I, in terms of each component parts by weight, including following components：
0.5 part～10 parts of aminated compoundss,
0 part～5 parts of alcohol compound；
B) inhibitor I is via alkali liquor injection line and the alkali liquor II of caustic wash tower together in on-line continuous injection caustic wash tower 1.
In technique scheme, described aminated compoundss are ethamine, diethylamine, triethylamine, ethylenediamine, propane diamine, Dan Yi
Hydramine, diethanolamine, triethanolamine, diglycolamine, isopropanolamine, N, N- diethyl ethylene diamine, azanol, N, N-
Dimethyl hydroxylamine, N, N- diethyl hydroxylamine, N- isopropylhydroxyla, N- t-butylhydroxylamine, methoxy propyl ammonia, ethylene amines,
Diethylenetriamine, triethylene tetramine, carbohydrazide, N, one or more of N- diformylhydrazine, N- methyl dimethoxy hydrazides mix
And thing；Described alcohol compound be isopropanol, propylene glycol, glycerol, MEHQ, 4- methoxyphenol, 2,6-
In ditertbutylparacresol, 2,6- DI-tert-butylphenol compounds, aminomethyl propanol, dimethylaminoethanol, diethylaminoethanol one
Plant or several mixture.
Butter inhibitor of the present invention, with amine, alcohol compound as raw material, is homogeneously dispersed in deionized water and is formed surely
Fixed solution system.The weight of aminated compoundss and alcohol compound is than for 1 (0.1～5).Aminated compoundss are preferably
The mixture of several aminated compoundss, the such as compositionss of diethylamine, dimethyl hydroxylamine and diethylenetriamine.Alcohol compound is excellent
Elect the mixture of several alcohol compounds as, such as the compositionss of aminomethyl propanol and isopropanol.Described butter inhibitor can also
Comprise only aminated compoundss.
Prepared butter inhibitor I injects line via the alkali liquor of caustic wash tower, and together on-line continuous are injected in caustic wash tower 1 with alkali liquor II,
Accounting for caustic wash tower charging III concentration after injection is 5～500ppm, preferably 25～200ppm.Caustic wash tower operation temperature be 30～
60 DEG C, pressure is 0.1～3.0MPa, and the preferred scope of temperature and pressure is respectively 35～50 DEG C, 0.5～2.0MPa.
The present invention is formation mechanism according to caustic wash tower butter come reasonable preparation butter inhibitor.The reason caustic wash tower butter generates
Mainly have two：In alkene generating process, aldoketoneses impurity easily occurs Aldol to be condensed in alkaline system, and that is, two molecules contain
The aldehydes or ketones having α-H are condensed and generate beta-hydroxy aldehyde, and then addition generates the clear yellow viscous polymer of certain molecular weight further；
And during some diolefins or other unsaturated hydrocarbon products also can induce in the presence of trace oxygen, metal ion from
By base, induction is crosslinked to generate polymer, is collectively referenced as butter with front described polymer.Accordingly, alcohols, amine chemical combination are added
The thing aldehyde ketone Aldol condensation in inhibition system simultaneously；Aminated compoundss can effectively suppress trace oxygen, metal ion to lure respectively
The alkene cross-linked polymeric sent out.After plant running 30 days, there are no stifled tower, and decrease discharge and the fresh soda of spent lye
The consume of liquid, reduces the environmental pollution causing because of butter discharge.
Below in conjunction with specific embodiment, the present invention is further elaborated.
Brief description
Fig. 1 is the schematic flow sheet of the method for the invention.
In Fig. 1,1 is methanol-to-olefins device caustic wash tower；Stream I is butter inhibitor；II is the alkali liquor thing of injection caustic wash tower
Stream；III is caustic wash tower feed stream；IV is caustic wash tower outlet streams；The salkali waste logistics that V discharges for caustic wash tower.
Specific embodiment
【Embodiment 1】
40g isopropylhydroxyla, 25g isopropanol are dissolved in 260g deionized water, after stirring, filter, filtrate is
Butter inhibitor, referred to as HYI-1.
Above-mentioned HYI-1 inhibitor is applied to methanol-to-olefins unit simulation caustic wash tower, caustic wash tower feed composition is ethylene
41.1%, propylene 40.2%, C411.2%, acetaldehyde 0.05%, butanone 0.03%, C5+ hydrocarbon 5.58%, CO20.02%,
Temperature 45 C, naoh concentration 10%.Using piston pump, inhibitor is added continuously in circulation alkali liquor enter alkali cleaning therewith
Tower, addition is 40ppm (with respect to caustic wash tower charging).After device continuously runs 30 days, have no stifled tower, calculate alkali
Butter weight in liquid.And compare with not adding the butter amount producing during butter inhibitor, suppression ratio is calculated according to following formula,
The results detailed in Table 1.
Suppression ratio=(1-m1/m2) × 100%
M in formula1For adding the butter amount producing in caustic wash tower after butter inhibitor, m2For not adding butter to press down under equal conditions
The butter amount producing during preparation.
【Embodiment 2】
Prepare butter inhibitor HYI-1 by embodiment 1 method, change addition 100ppm of butter inhibitor, equally press
Embodiment 1 method evaluates the inhibition that it generates to butter, refers to table 1.
【Embodiment 3】
Prepare butter inhibitor HYI-1 by embodiment 1 method, change addition 200ppm of butter inhibitor, equally press
Embodiment 1 method evaluates the inhibition that it generates to butter, refers to table 1.
【Embodiment 4】
Prepare butter inhibitor HYI-1 by embodiment 1 method, change addition 400ppm of butter inhibitor, equally press
Embodiment 1 method evaluates the inhibition that it generates to butter, refers to table 1.
【Embodiment 5】
Change component and each component addition, deionized water 300g, diglycolamine 40g, 1,3-PD 50g.By enforcement
Example 1 method is prepared butter inhibitor HYI-2 and is equally evaluated its inhibition to butter generation by embodiment 1 method, in detail
It is shown in Table 1.
【Embodiment 6】
Change component and each component addition, deionized water 300g, ethylenediamine 30g, dimethylaminoethanol 25g.By enforcement
Example 1 method is prepared butter inhibitor HYI-3 and is equally evaluated its inhibition to butter generation by embodiment 1 method, in detail
It is shown in Table 1.
【Embodiment 7】
Change component and each component addition, deionized water 280g, ethamine 10g, N, N- dimethyl hydroxylamine 28g, diformazan
Ethylaminoethanol 30g.Prepare butter inhibitor HYI-4 by embodiment 1 method and equally evaluate it to Huang by embodiment 1 method
The inhibition that oil generates, refers to table 1.
【Embodiment 8】
Change component and each component addition, deionized water 280g, ethamine 10g, N, N- dimethyl hydroxylamine 28g, second two
Amine 22g, 1,3-PD 30g.Prepare butter inhibitor HYI-5 by embodiment 1 method and equally by embodiment 1 method
Evaluate its inhibition to butter generation, refer to table 1.
【Embodiment 9】
Change component and each component addition, deionized water 300g, diethylamine 10g, N, N- dimethyl hydroxylamine 28g, diethyl
Alkene triamine 22g, aminomethyl propanol 15g, isopropanol 30g.Prepare butter inhibitor HYI-6 by embodiment 1 method simultaneously same
Evaluate its inhibition to butter generation by embodiment 1 method, refer to table 1.
【Comparative example 1】
Add existing butter inhibitor HYI-7, by the examination of embodiment 1 method, the results detailed in Table 1.
Table 1
Claims (10)
1. a kind of method that suppression butter generates, comprises the following steps：
A) adopt a kind of butter inhibitor (I), in terms of each component parts by weight, including following components：
0.5 part～10 parts of aminated compoundss,
0 part～5 parts of alcohol compound；
B) inhibitor (I) injects line and alkali liquor (II) together on-line continuous injection caustic wash tower (1) via the alkali liquor of caustic wash tower
In.
2. according to claim 1 suppression butter generate method it is characterised in that aminated compoundss be ethamine, diethylamine,
Triethylamine, ethylenediamine, propane diamine, monoethanolamine, diethanolamine, triethanolamine, diglycolamine, isopropanolamine, N,
N- diethyl ethylene diamine, azanol, N, N- dimethyl hydroxylamine, N, N- diethyl hydroxylamine, N- isopropylhydroxyla, uncle N-
Butylhydroxylamine, methoxy propyl ammonia, ethylene amines, diethylenetriamine, triethylene tetramine, carbohydrazide, N, N- bis- formyl
One or more of hydrazine, N- methyl dimethoxy hydrazides mixture.
3. suppression butter according to claim 1 generates method it is characterised in that alcohol compound be isopropanol, the third two
Alcohol, glycerol, MEHQ, 4- methoxyphenol, 2,6 ditertiary butyl p cresol, 2,6- di-tert-butyl
One or more of phenol, aminomethyl propanol, dimethylaminoethanol, diethylaminoethanol mixture.
4. suppression butter according to claim 1 generates method is it is characterised in that aminated compoundss and alcohol compound
Weight is than for 1 (0.1～5).
5. the method that suppression butter according to claim 1 generates is it is characterised in that solvent is deionized water.
6. the method that suppression butter according to claim 1 generates is it is characterised in that aminated compoundss are diethylamine, diformazan
Base azanol and the compositionss of diethylenetriamine, alcohol compound is the compositionss of aminomethyl propanol and isopropanol.
7. the method that suppression butter according to claim 1 generates is it is characterised in that each component is evenly dispersed in deionization
Form stable solution system in water.
8. the method that suppression butter according to claim 1 generates is it is characterised in that butter inhibitor (I) is via caustic wash tower
Alkali liquor injection line and alkali liquor (II) together in on-line continuous injection caustic wash tower (1).
9. the method that suppression butter according to claim 1 generates is it is characterised in that account for caustic wash tower after butter inhibitor injection
Charging (III) concentration is 5～500ppm.
10. according to claim 9 suppression butter generate method it is characterised in that caustic wash tower operation temperature be 30～60 DEG C,
Pressure is 0.1～3.0MPa.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109879715A (en) * | 2019-02-22 | 2019-06-14 | 广昌达新材料技术服务（深圳）股份有限公司 | Butter inhibitor and its preparation method and application |
| CN110452733A (en) * | 2018-05-08 | 2019-11-15 | 中国石油化工股份有限公司 | Inhibit the butter inhibitor that butter generates in MTO caustic wash tower |
| CN111056892A (en) * | 2018-10-17 | 2020-04-24 | 中国石油化工股份有限公司 | Grease inhibitor for alkaline washing tower of methanol-to-olefin device |
| CN111056907A (en) * | 2018-10-17 | 2020-04-24 | 中国石油化工股份有限公司 | Butter inhibitor of alkaline washing system of methanol-to-olefin device |
| CN112004789A (en) * | 2018-04-25 | 2020-11-27 | 利安德化学技术有限公司 | Method and device for purifying crude propane |
| CN112210381A (en) * | 2019-07-10 | 2021-01-12 | 中国石油化工股份有限公司 | Inhibitor composition, preparation method and application thereof |
| CN112209801A (en) * | 2019-07-10 | 2021-01-12 | 中国石油化工股份有限公司 | Method for inhibiting pressure difference rise of alkaline washing tower for preparing low-carbon olefins from methanol |
| WO2022042278A1 (en) * | 2020-08-24 | 2022-03-03 | Ecolab Usa Inc. | A multifunctional antifoulant for coal to olefins caustic tower antifouling |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112004789A (en) * | 2018-04-25 | 2020-11-27 | 利安德化学技术有限公司 | Method and device for purifying crude propane |
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| CN112209801B (en) * | 2019-07-10 | 2022-07-12 | 中国石油化工股份有限公司 | Method for inhibiting pressure difference rise of alkaline washing tower for preparing low-carbon olefins from methanol |
| CN112209801A (en) * | 2019-07-10 | 2021-01-12 | 中国石油化工股份有限公司 | Method for inhibiting pressure difference rise of alkaline washing tower for preparing low-carbon olefins from methanol |
| CN112210381A (en) * | 2019-07-10 | 2021-01-12 | 中国石油化工股份有限公司 | Inhibitor composition, preparation method and application thereof |
| WO2022042278A1 (en) * | 2020-08-24 | 2022-03-03 | Ecolab Usa Inc. | A multifunctional antifoulant for coal to olefins caustic tower antifouling |
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