CN106467444B - The method for inhibiting butter to generate - Google Patents
The method for inhibiting butter to generate Download PDFInfo
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- CN106467444B CN106467444B CN201510514404.7A CN201510514404A CN106467444B CN 106467444 B CN106467444 B CN 106467444B CN 201510514404 A CN201510514404 A CN 201510514404A CN 106467444 B CN106467444 B CN 106467444B
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- butter
- caustic wash
- wash tower
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- lye
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Abstract
The present invention relates to a kind of method that inhibition butter generates, mainly solve butter inhibitory effect in previous caustic wash tower it is bad, it is unstable lead to stifled tower, operate relatively complicated, the technical problems such as higher cost.The present invention, which passes through, a) uses a kind of butter inhibitor (I), in terms of each component parts by weight, including following components: 0.5 part~10 parts of aminated compounds, 0 part~5 parts of alcohol compound；B) lye injection line of the inhibitor (I) via caustic wash tower and the technical solution in lye (II) together on-line continuous injection caustic wash tower (1), solves above-mentioned technical problem, the a large amount of generations that can be used for inhibiting butter in the commercial plants caustic wash tower such as petroleum ethylene, producing ethylene with ethyl alcohol, methanol-to-olefins, vinyl acetate, dichloroethylene, propylene oxide even cause stifled tower.
Description
Technical field
The present invention relates to a kind of methods that inhibition butter generates.
Background technique
Ethylene and propylene are important Organic Chemicals in low-carbon alkene, and demand increases year by year.Tradition acquisition ethylene,
The route of propylene is naphtha pyrolysis, this route relies on petroleum, and petroleum has rise in price in a short time, supplies unstable ask
Topic, there is the problems such as resource storage capacity is limited for a long time.Therefore in recent years as the work for being most hopeful substitution naphtha route alkene
Skill, coal or natural gas have obtained greatly via the low-carbon alkenes such as methanol ethylene, propylene technology (methanol-to-olefins, MTO or MTP)
Concern.Either in traditional naphtha pyrolysis route or in emerging methanol-to-olefins technology, accord in order to obtain
It closes the target product of purity requirement or recycles certain unreacted materials, the material flowed out from reactor is all needed by a series of
Isolation of purified process, and in order to remove the caustic wash tower of acid impurities be then one of the key equipment of material purification.Caustic wash tower one
As using sodium hydrate aqueous solution as medium, when the aldoketones impurity generated in methanol to olefins reaction pass through caustic wash tower when in alkalinity
Aldol condensation easily occurs under solution catalyzing, i.e. two molecules generate beta-hydroxy aldehyde with the aldehydes or ketones condensation of α-H, then into one
Walk the clear yellow viscous polymer that addition forms certain molecular weight.In addition, certain diolefins or other unsaturated hydrocarbons in reaction process
Class product can also induce free radical under the action of trace oxygen, metal ion, induce crosslinking and generate polymer, and preceding described poly-
It closes object and is collectively referenced as butter.Butter seriously reduces the alkali cleaning effect of caustic wash tower, consumes a large amount of lye, and it is stifled to be easy polymerization fouling
Sai Tanei distributor and filler cause stifled tower, shorten the cycle of operation of caustic wash tower.And the salkali waste outlet containing a large amount of butter, it will
Difficulty is brought to the operation of downstream processing facility and generates serious environmental pollution.
Solving the method that a large amount of butter of caustic wash tower generate at present mainly has transformation caustic wash tower, optimization alkali cleaning operation and addition yellow
Oily inhibitor.Transformation caustic wash tower, optimization alkali cleaning operation can improve alkali cleaning effect, extend the device cycle of operation, but cannot be from basic
Upper inhibition butter generates.Addition butter inhibitor can greatly reduce the generation of butter, while can also make the butter generated as early as possible
It is distributed in lye with lye discharger, avoids serious environmental pollution, and use easy, small investment.Patent
US5879534 is disclosed in dichloroethylene production process, and being added on α-C does not have the carbonyls such as formaldehyde, second two of active H
Aldehyde, benzaldehyde, formic acid, ethanedioic acid, paraformaldehyde, P-methoxybenzal-dehyde etc. make it first react poly- to inhibit to be formed with acetaldehyde
Close object.Patent US6986839 discloses a kind of generation for inhibiting butter in petroleum installation caustic wash tower with amino acids.Specially
Sharp CN101348410A is by a kind of ternary mixture being made of alcamines, hydrazides, alkyl amine come ethene suppressing dress
Set butter in caustic wash tower.Patent US5264114 discloses a kind of aminated compounds RNH2And R2NH carrys out ethene suppressing device alkali cleaning
The generation of butter in tower, wherein R is alkyl or aromatic radical.It with molecular formula is X- (R) that patent US5900495, which is disclosed a kind of,n-X1
Aminated compounds inhibit propylene oxide unit caustic wash tower in acetaldehyde polymerization, wherein X be amido or the alkane containing 1~5 carbon
Amido, X1For hydrogen, hydroxyl, amido or alkylamino radical containing 1~5 carbon；N is 1~4；R is-CH2NH-, arlydene or contain 2~10
The alkyl of carbon.
The butter suppressing method of methanol-to-olefins device caustic wash tower is not specifically mentioned in above-mentioned patent, and specific aim is not
By force, inhibitor using effect is bad, unstable, operates relatively complicated, higher cost.
Summary of the invention
In the method generated the technical problem to be solved by the present invention is to existing inhibition butter, to methanol-to-olefins device alkali
The problems such as specific aim for washing tower is not strong, and inhibitor using effect is bad, unstable, and operation is relatively complicated, higher cost.The present invention
The suppressing method that butter generates in a kind of methanol-to-olefins device caustic wash tower is provided, this method is also not limited to methanol-to-olefins dress
Caustic wash tower is set, also can operate with petroleum ethylene, producing ethylene with ethyl alcohol, preparing propylene from methanol, vinyl acetate, dichloroethylene, propylene oxide
In equal commercial plants caustic wash tower.
In order to solve the above-mentioned technical problem, technical scheme is as follows: a method of inhibit butter to generate, including
Following steps:
A) a kind of butter inhibitor I is used, in terms of each component parts by weight, including following components:
0.5 part~10 parts of aminated compounds,
0 part~5 parts of alcohol compound；
B) inhibitor I injects in caustic wash tower 1 via lye injection line on-line continuous together with lye II of caustic wash tower.
In above-mentioned technical proposal, the aminated compounds is ethamine, diethylamine, triethylamine, ethylenediamine, propane diamine, Dan Yi
Hydramine, diethanol amine, triethanolamine, diglycolamine, isopropanolamine, N, N- diethyl ethylene diamine, azanol, N, N- dimethyl hydroxyl
Amine, N, N- diethyl hydroxylamine, N- isopropylhydroxyla, N- t-butylhydroxylamine, methoxy propyl ammonia, ethylene amines, diethylenetriamine, three
Ethylene tetramine, carbohydrazide, N, one or more of N- diformylhydrazine, N- methyl dimethoxy hydrazides mixture；The alcohols chemical combination
Object is isopropanol, propylene glycol, glycerine, p-hydroxyanisole, 4- metoxyphenol, 2,6-di-tert-butyl p-cresol, 2,6- bis-
One or more of tert-butyl phenol, aminomethyl propanol, dimethylaminoethanol, diethylaminoethanol mixture.
Butter inhibitor of the present invention is homogeneously dispersed in shape in deionized water using amine, alcohol compound as raw material
At stable solution system.The weight ratio of aminated compounds and alcohol compound is 1 ︰ (0.1~5).Aminated compounds is preferably
The mixture of several aminated compounds, such as the composition of diethylamine, dimethyl hydroxylamine and diethylenetriamine.Alcohol compound is preferred
For the mixture of several alcohol compounds, such as the composition of aminomethyl propanol and isopropanol.The butter inhibitor can also be only
Contain aminated compounds.
Butter inhibitor I obtained injects caustic wash tower via lye injection line on-line continuous together with lye II of caustic wash tower
It is 5~500ppm, preferably 25~200ppm that caustic wash tower charging III concentration is accounted in 1, after injection.Caustic wash tower operation temperature is 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 according to the formation mechanism of caustic wash tower butter come reasonable preparation butter inhibitor.What caustic wash tower butter generated
Reason mainly has two: in alkene generating process, Aldol condensation, i.e. two molecules easily occur in alkaline system for aldoketones impurity
Aldehydes or ketones condensation containing α-H generates beta-hydroxy aldehyde, and then further addition generates the clear yellow viscous polymer of certain molecular weight；
And certain diolefins or other unsaturated hydrocarbon products in the process can also induce certainly under the action of trace oxygen, metal ion
By base, induces crosslinking and generate polymer, be collectively referenced as butter with the preceding polymer.Accordingly, it is same that alcohols, aminated compounds is added
When inhibition system in aldehyde ketone Aldol condensation；The alkene that aminated compounds can effectively inhibit trace oxygen, metal ion to induce respectively
Hydrocarbon cross-linked polymeric.After device is run 30 days, stifled tower there are no, and reduce the discharge of spent lye and the consume of fresh lye,
Environmental pollution caused by reducing because of butter discharge.
Below in conjunction with specific embodiment, the present invention is further elaborated.
Detailed description of the invention
Fig. 1 is the flow diagram 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 lye for injecting caustic wash tower
Logistics；III is caustic wash tower feed stream；IV is caustic wash tower outlet streams；V is the salkali waste logistics of caustic wash tower discharge.
Specific embodiment
[embodiment 1]
40g isopropylhydroxyla, 25g isopropanol are dissolved in 260g deionized water, after mixing evenly, filtered, 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
DEG C, naoh concentration 10%.Inhibitor is added continuously in circulation alkali liquor using piston pump to enter caustic wash tower therewith, is added
Amount is 40ppm (feeding relative to caustic wash tower).After device continuously runs 30 days, stifled tower is had no, calculate the butter weight in lye.
And compared with the butter amount generated when butter inhibitor not being added, inhibiting rate is calculated according to the following formula, as a result see Table 1 for details.
Inhibiting rate=(1-m1/m2) × 100%
M in formula1For the butter amount generated in caustic wash tower after addition butter inhibitor, m2For butter is not added under equal conditions
The butter amount generated when inhibitor.
[embodiment 2]
Butter inhibitor HYI-1 is prepared by 1 method of embodiment, changes the additional amount 100ppm of butter inhibitor, equally presses
1 method of embodiment evaluates its inhibitory effect generated to butter, and see Table 1 for details.
[embodiment 3]
Butter inhibitor HYI-1 is prepared by 1 method of embodiment, changes the additional amount 200ppm of butter inhibitor, equally presses
1 method of embodiment evaluates its inhibitory effect generated to butter, and see Table 1 for details.
[embodiment 4]
Butter inhibitor HYI-1 is prepared by 1 method of embodiment, changes the additional amount 400ppm of butter inhibitor, equally presses
1 method of embodiment evaluates its inhibitory effect generated to butter, and see Table 1 for details.
[embodiment 5]
Change component and each component additional amount, deionized water 300g, diglycolamine 40g, 1,3-PD 50g.By implementation
1 method of example prepares butter inhibitor HYI-2 and equally evaluates its inhibitory effect generated to butter by 1 method of embodiment, is detailed in
Table 1.
[embodiment 6]
Change component and each component additional amount, deionized water 300g, ethylenediamine 30g, dimethylaminoethanol 25g.By implementation
1 method of example prepares butter inhibitor HYI-3 and equally evaluates its inhibitory effect generated to butter by 1 method of embodiment, is detailed in
Table 1.
[embodiment 7]
Change component and each component additional amount, deionized water 280g, ethamine 10g, N, N- dimethyl hydroxylamine 28g, diformazan ammonia
Base ethyl alcohol 30g.It is prepared butter inhibitor HYI-4 by 1 method of embodiment and is equally evaluated it by 1 method of embodiment and butter is generated
Inhibitory effect, see Table 1 for details.
[embodiment 8]
Change component and each component additional amount, deionized water 280g, ethamine 10g, N, N- dimethyl hydroxylamine 28g, ethylenediamine
22g, 1,3-PD 30g.Butter inhibitor HYI-5 is prepared by 1 method of embodiment and equally to evaluate its by 1 method of embodiment right
The inhibitory effect that butter generates, see Table 1 for details.
[embodiment 9]
Change component and each component additional amount, deionized water 300g, diethylamine 10g, N, N- dimethyl hydroxylamine 28g, diethyl
Alkene triamine 22g, aminomethyl propanol 15g, isopropanol 30g.Butter inhibitor HYI-6 is prepared by 1 method of embodiment and equally by reality
It applies 1 method of example and evaluates its inhibitory effect generated to butter, see Table 1 for details.
[comparative example 1]
Existing butter inhibitor HYI-7 is added, is checked and rated by 1 method of embodiment, as a result see Table 1 for details.
Table 1
Claims (5)
1. a kind of method for inhibiting butter to generate, comprising the following steps:
A) a kind of butter inhibitor (I) is used, including following components:
Aminated compounds, aminated compounds be diethylamine, N, the composition of N- dimethyl hydroxylamine and diethylenetriamine,
Alcohol compound, alcohol compound are the composition of aminomethyl propanol and isopropanol,
The weight ratio of aminated compounds and alcohol compound is 1 ︰ (0.1~5)；
B) inhibitor (I) is yellow via the lye injection line and lye (II) of caustic wash tower together in on-line continuous injection caustic wash tower (1)
It is 5~500ppm that caustic wash tower charging (III) concentration is accounted for after oily inhibitor injection.
2. the method according to claim 1 for inhibiting butter to generate, it is characterised in that solvent is deionized water.
3. it is according to claim 1 inhibit butter generate method, it is characterised in that each component be evenly dispersed in from
Stable solution system is formed in sub- water.
4. the method according to claim 1 for inhibiting butter to generate, it is characterised in that butter inhibitor (I) is via caustic wash tower
Lye injection line and lye (II) together on-line continuous injection caustic wash tower (1) in.
5. the method according to claim 1 for inhibiting butter to generate, it is characterised in that caustic wash tower operation temperature is 30~60
DEG C, pressure is 0.1~3.0MPa.
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019209953A1 (en) * | 2018-04-25 | 2019-10-31 | Lyondell Chemical Technology, L.P. | Methods and apparatuses for purifying crude propane |
| 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 |
| CN111056907B (en) * | 2018-10-17 | 2023-05-02 | 中国石油化工股份有限公司 | Butter inhibitor of alkaline washing system of methanol-to-olefin device |
| CN111056892B (en) * | 2018-10-17 | 2023-04-07 | 中国石油化工股份有限公司 | Grease inhibitor for alkaline washing tower of methanol-to-olefin device |
| CN109879715B (en) * | 2019-02-22 | 2022-07-29 | 广昌达新材料技术服务（深圳）股份有限公司 | Butter inhibitor and preparation method and application thereof |
| 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 |
| CN112210381B (en) * | 2019-07-10 | 2023-04-07 | 中国石油化工股份有限公司 | Inhibitor composition, preparation method and application thereof |
| CN114084968A (en) * | 2020-08-24 | 2022-02-25 | 埃科莱布美国股份有限公司 | Multifunctional antifouling agent for coal-to-olefin alkali tower antifouling |
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| US1649983A (en) * | 1924-12-20 | 1927-11-22 | Burgess Lab Inc C F | Veneer core |
| CN101348410A (en) * | 2008-09-10 | 2009-01-21 | 北京斯伯乐科学技术研究院 | Ethylene apparatus caustic wash tower butter inhibitor and use method thereof |
| CN102875306A (en) * | 2011-07-12 | 2013-01-16 | 中国石油化工股份有限公司 | Method for inhibiting grease in alkaline washing towers |
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