CN109879715A - Butter inhibitor and its preparation method and application - Google Patents
Butter inhibitor and its preparation method and application Download PDFInfo
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Abstract
The present invention relates to a kind of butter inhibitors and its preparation method and application.A kind of butter inhibitor, according to mass fraction meter, including 20 parts~35 parts of acetoacetic esters, 15 parts~25 parts of NO free radical, 1 part~10 parts of polycarboxylate, 5 parts~15 parts of polyethenoxy ether class compound and 15 parts~40 parts of diluent, wherein, the general structure of acetoacetic ester is CH3COCH2COOCnHm, wherein n is the arbitrary integer in 1~10, and m is the arbitrary integer in 3~21；NO free radical is piperidine nitroxide free-radical.Above-mentioned butter inhibitor has the advantages that stable homogeneous, preferable to butter inhibitory effect in water phase and oily phase.
Description
Technical field
The present invention relates to ethylene preparation fields, more particularly to a kind of butter inhibitor and its preparation method and application.
Background technique
During hydrocarbon cracking ethylene industry, the gas for being largely easily converted into acidic materials is inevitably resulted from,
Predominantly H2S、CO2Deng can corrode equipment, cause subsequent cryogenic separation and rectifier unit if the acidic materials of generation are not removed
Blocking, cause catalyst poisoning in ethylene polymerisation process and pollute ethylene.Therefore, ethylene producing device be typically provided amine wash and
Caustic washing system removes acidic materials.But under strong basicity environment, Aldol condensation can occur for the substances such as aldehyde, ketone in cracking gas
Reaction generates polymer, and in addition free radical polymerization can also occur for the active olefin in cracking gas, adds high relative molecular mass
Hydro carbons condense, eventually form by the butter based on aldehyde, ketone condensation polymer and olefin polymer.A large amount of butter will affect alkali
The normal operation and alkali cleaning effect of tower are washed, and consumes a large amount of lye, while the easy polymerization fouling of butter blocks distributor in tower and fills out
Material causes stifled tower phenomenon, shortens the cycle of operation of caustic wash tower；In addition, the salkali waste outlet containing a large amount of butter, sets to downstream processing
The operation applied brings difficulty, influences environment protection emission index.
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 and optimization alkali cleaning operation can improve alkali cleaning effect, extend the device cycle of operation, but cannot be from root
Inhibit the generation of butter in sheet.Addition butter inhibitor can greatly reduce the generation of butter, while can also make the butter generated
It is distributed in lye as early as possible, with spent lye discharger, the method for being presently the most simple and effective and generally using, and solve
The development trend of butter problem.But traditional butter inhibitor is difficult to take into account inhibition water phase while forming stable homogeneous system
It is condensed with aldehyde, the ketone in oily phase, and inhibitory effect is poor.
Summary of the invention
Based on this, it is necessary to provide a kind of stable homogeneous, to the preferable butter of butter inhibitory effect in water phase and oily phase
Inhibitor.
In addition, additionally providing a kind of preparation method and application of butter inhibitor.
A kind of butter inhibitor, according to mass fraction meter, including
Wherein, the general structure of the acetoacetic ester is CH3COCH2COOCnHm, wherein n is any whole in 1~10
Number, m are the arbitrary integer in 3~21；The NO free radical is piperidine nitroxide free-radical.
The prescription science of above-mentioned butter inhibitor, proportion rationally, acetoacetic ester and NO free radical can coordinated,
The generation for preventing butter in terms of inhibiting aldehyde, ketone polycondensation and inhibition olefinic polymerization two respectively, to make the suppression of butter inhibitor
Effect processed is preferable；Polycarboxylate can be such that the part butter generated dissolution is dispersed in lye, avoid butter from being adhered to as far as possible
In equipment and in pipeline；Polyethenoxy ether class compound and polycarboxylate act synergistically, and make the emulsification point of butter inhibitor each component
Stable homogeneous system is dissipated and formed, stable microemulsion can be formed in water phase and oily phase, to make butter inhibitor to water
Mutually and the aldehyde in oily phase, ketone polycondensation reaction have inhibiting effect.Therefore, above-mentioned butter inhibitor has stable homogeneous, to water phase
The preferable advantage with butter inhibitory effect in oily phase.
The acetoacetic ester is selected from methyl acetoacetate, ethyl acetoacetate, acetyl second in one of the embodiments,
At least one of propyl propionate, butyl-acetoacetate and acetoacetic acid allyl ester.
The NO free radical is selected from 2,2,6,6- tetramethyl piperidine -1- oxygen radicals, 4- in one of the embodiments,
In hydroxyl -2,2,6,6- tetramethyl piperidine -1- oxygen radical and 4- oxygen -2,2,6,6- tetramethyl piperidine -1- oxygen radical extremely
Few one kind.
In one of the embodiments, the polycarboxylate in Sodium Polyacrylate and sodium polymethacrylate at least
It is a kind of.
The polyethenoxy ether class compound is selected from dodecyl phenol polyethenoxy ether, loses in one of the embodiments,
Water sorbitol monooleate polyoxyethylene ether, sorbitan monostearate polyoxyethylene ether, ethoxylated dodecyl alcohol and
At least one of lauric alcohol polyoxyethylene ether.
It in one of the embodiments, further include the hydroxyl amine compound that mass fraction is 20 parts~35 parts, the hydroxyl
The general structure of base aminated compounds is R1(R2)N-(CH2)k- OH, wherein R1And R2Separately it is selected from hydrogen, carbon atom number
One of the aralkyl that alkyl and carbon atom number for 1~10 are 7~15, k are the arbitrary integer in 0~8.
It in one of the embodiments, further include the dialkyl group ketoxime that mass fraction is 1 part~15 parts.
It in one of the embodiments, further include the alkylhydroxyoximate that mass fraction is 1 part~15 parts, the alkyl hydroxyl
The general structure of oxime hydrochlorate is RCONHONa, wherein R is the alkyl that carbon atom number is 4~9.
A kind of preparation method of butter inhibitor, comprising steps of
According to mass fraction meter, by 20 parts~35 parts of acetoacetic ester, 15 parts~25 parts of NO free radical, 1 part~
10 parts of polycarboxylate, 5 parts~15 parts of polyethenoxy ether class compound and the mixing of 15 parts~40 parts of diluent, obtain butter
Inhibitor, wherein the general structure of the acetoacetic ester is CH3COCH2COOCnHm, wherein n is any whole in 1~10
Number, m are the arbitrary integer in 3~21；The NO free radical is piperidine nitroxide free-radical.
It is prepared by butter inhibitor made from the preparation method of above-mentioned butter inhibitor or above-mentioned butter inhibitor
Application in ethylene.
Specific embodiment
The invention can be realized in many different forms, however it is not limited to embodiment described herein.On the contrary, mentioning
Purpose for these embodiments is to make the disclosure of the present invention more thorough and comprehensive.
Unless otherwise defined, all technical and scientific terms used herein and belong to technical field of the invention
The normally understood meaning of technical staff is identical.Term as used herein in the specification of the present invention is intended merely to description tool
Body embodiment purpose, it is not intended that in limitation the present invention.
The butter inhibitor of one embodiment, according to mass fraction meter, including
Acetoacetic ester under alkaline condition can with aldehyde, ketone carry out condensation reaction, generate not polymerization activity stablize it is small
Molecular compound and be dissolved in lye, and reaction process is irreversible, and the aldehyde in lye, ketone is fundamentally inhibited to occur
Aldol polycondensation reaction.Further, the general structure of acetoacetic ester is CH3COCH2COOCnHm, wherein n is in 1~10
Arbitrary integer, m are the arbitrary integer in 3~21.Further, the mass fraction of acetoacetic ester is 22 parts~30 parts.
Specifically, acetoacetic ester is selected from methyl acetoacetate, ethyl acetoacetate, propyl acetoacetate, acetoacetate
At least one of butyl ester and acetoacetic acid allyl ester.More specifically, acetoacetic ester is selected from methyl acetoacetate and acetyl second
At least one of acetoacetic ester.
NO free radical is a kind of highly stable new free-radical polymerization inhibitor, does not cause monomer not only and generates new freedom
Base, moreover it is possible to which effectively capture living radical generates stable molecule-type compound, to have the function that inhibit completely.Into one
Step ground, the mass fraction of NO free radical are 18 parts~22 parts.Specifically, NO free radical is piperidine nitroxide free-radical.More
Specifically, NO free radical is selected from 2,2,6,6- tetramethyl piperidine -1- oxygen radicals, 4- hydroxyl -2,2,6,6- tetramethyl piperidines -
At least one of 1- oxygen radical and 4- oxygen -2,2,6,6- tetramethyl piperidine -1- oxygen radical.
The butter that polycarboxylate has generated caustic wash tower inside has dissolution peptizaiton, makes the part butter generated
It can be dissolved in lye, butter is avoided to be adhered in equipment and in pipeline as far as possible, for stablizing caustic wash tower operation, extending caustic wash tower
Operation cycle has better effects.Further, the mass fraction of polycarboxylate is 3 parts~8 parts.Specifically, polycarboxylate selects
From at least one of Sodium Polyacrylate and sodium polymethacrylate.More specifically, the number-average molecular weight of polycarboxylate is 1000
~5000.In one embodiment, polycarboxylate is the Sodium Polyacrylate that number-average molecular weight is 2000~3000.
Polyethenoxy ether class compound and polycarboxylate act synergistically, and make each component emulsion dispersion and shape in butter inhibitor
At stable homogeneous system, stable microemulsion can be formed in water phase and oily phase, to make butter inhibitor to water phase and oil
Aldehyde, ketone polycondensation reaction in phase have inhibiting effect.Further, the mass fraction of polyethenoxy ether class compound be 8 parts~
12 parts.Specifically, polyethenoxy ether class compound is selected from dodecyl phenol polyethenoxy ether, sorbitan monooleate polyoxy
In vinethene, sorbitan monostearate polyoxyethylene ether, ethoxylated dodecyl alcohol and lauric alcohol polyoxyethylene ether
It is at least one.
Further, the number-average molecular weight of polyethenoxy ether class compound is 1000~5000.Further, polyoxy second
Alkene ether compound is selected from the sorbitan monooleate polyoxyethylene ether that number-average molecular weight is 2000~3000 and number is divided equally
At least one of the lauric alcohol polyoxyethylene ether that son amount is 2000~3000.
Further, the mass fraction of diluent is 20 parts~35 parts.Specifically, diluent is water.More specifically, dilution
Agent is deionized water.
It should be noted that butter inhibitor further includes the hydroxyl amine compound that mass fraction is 20 parts~35 parts.Hydroxyl
Base aminated compounds contains reactive hydrogen atom, can be condensed with aldehyde, ketone, new stabilized radical can also be generated with radical reaction,
Aldehyde, ketone polycondensation and alkene cross-linking polymerization can effectively be inhibited simultaneously.Further, the mass fraction of hydroxyl amine compound
It is 22 parts~30 parts.Specifically, the general structure of hydroxyl amine compound is R1(R2)N-(CH2)k- OH, wherein R1And R2Respectively
Independently selected from hydrogen, carbon atom number be 1~10 alkyl and carbon atom number be 7~15 one of aralkyl, k be 0~8 in
Arbitrary integer.
Further, hydroxyl amine compound is selected from N, N- diethyl hydroxylamine, N- isopropylhydroxyla, N, N- dibenzyl hydroxyl
At least one of amine, monoethanolamine, triethanolamine and triisopropanolamine.Further, hydroxyl amine compound is selected from N,
At least one of N- diethyl hydroxylamine, N- isopropylhydroxyla and monoethanolamine.
It should be noted that butter inhibitor further includes the dialkyl group ketoxime that mass fraction is 1 part~15 parts.Dialkyl ketone
Oxime has stronger reproducibility, can quickly react with the trace oxygen in lye, reduces the dissolved oxygen content in lye, and deoxygenation is completeer
Entirely, so as to effectively reduce the generation of free radical, inhibit the formation of cross-linked polymer；Meanwhile dialkyl group ketoxime also has anti-corrosion
Effect, the corrosion product capable of washing being deposited at caustic wash tower, and good magnetic oxide protective film is formed in metal surface, it is blunt
Change metal surface, effectively delays the corrosion of caustic wash tower.Further, the mass fraction of dialkyl group ketoxime is 5 parts~10 parts.Specifically
Ground, dialkyl group ketoxime in dimethyl ketone oxime, methyl ethyl ketone oxime, methyl-propyl ketoxime and methyl isobutyl ketoxime at least
It is a kind of.
It should be noted that butter inhibitor further includes the alkylhydroxyoximate that mass fraction is 1 part~15 parts.Alkyl hydroxyl
There is oxygen and nitrogen containing lone pair electrons in oxime hydrochlorate molecular structure, and position is close to each other, the structure enable it to and metal from
Son chelating generates stable chelate, prevents the catalytic action of metal ion, and then inhibit the formation of cross-linked polymer.Further
Ground, the mass fraction of alkylhydroxyoximate are 5 parts~10 parts.Wherein, the general structure of alkylhydroxyoximate is RCONHONa,
In, R is the alkyl that carbon atom number is 4~9.Specifically, the alkylhydroxyoximate is selected from octyl sodium alkyl hydroxamate, cyclohexyl methyl hydroxyl
At least one of oxime acid sodium and nonyl sodium alkyl hydroxamate.
In one of the embodiments, in terms of mass fraction, butter inhibitor includes:
It is generally believed that caustic washing system butter generates tool there are two reason: first is that cracking gas condenses or molten in alkaline cleaning procedure
Diolefin or other unsaturated hydrocarbons of the solution in lye form free radical under the action of trace oxygen, metal ion, for crosslinking
The formation of polymer provides initiation conditions.Second is that the aldehydes or ketones in cracking gas are in the presence of alkali, Yi Yinqi Aldol condensation is anti-
It answers, is i.e. has the aldehydes or ketones of reactive hydrogen atom under NaOH effect on two molecule alpha position carbon atoms, addition reaction generates beta-hydroxy aldehyde,
Then the polymer of certain molecular weight, i.e. butter are further added to.
Above-mentioned butter inhibitor at least has the advantages that
1) the prescription science of above-mentioned butter inhibitor, rationally, acetoacetic ester and NO free radical can cooperate with and match proportion
It closes, the generation of butter is prevented in terms of inhibiting aldehyde, ketone polycondensation and inhibition olefinic polymerization two respectively, to make butter inhibitor
Inhibitory effect is preferable；Polycarboxylate can be such that the part butter generated dissolution is dispersed in lye, avoid butter from adhering to as far as possible
In equipment and in pipeline；Polyethenoxy ether class compound and polycarboxylate act synergistically, and emulsify butter inhibitor each component
Disperse and formed stable homogeneous system, stable microemulsion can be formed in water phase and oily phase, to make butter inhibitor pair
Water phase and the aldehyde in oily phase, ketone polycondensation reaction have inhibiting effect.Therefore, above-mentioned butter inhibitor has stable homogeneous, to water
The mutually advantage preferable with butter inhibitory effect in oily phase.
2) butter inhibitor further includes hydroxyl amine compound, and hydroxyl amine compound contains reactive hydrogen atom, can not only
It is condensed with aldehyde, ketone, and new stabilized radical can be generated with radical reaction, therefore, hydroxyl amine compound can be with acetyl
Acetic acid esters and NO free radical coordinated, while effectively inhibiting aldehyde, ketone polycondensation and alkene cross-linking polymerization, so that butter presses down
The inhibitory effect of preparation is more preferable.
3) butter inhibitor further includes dialkyl group ketoxime, and dialkyl group ketoxime has stronger reproducibility, can be quickly and in lye
Trace oxygen reaction, reduce lye in dissolved oxygen content, deoxygenation is more complete, so as to effectively reduce the generation of free radical, suppression
The formation of cross-linked polymer processed；Meanwhile dialkyl group ketoxime also has antisepsis, the corrosion capable of washing being deposited at caustic wash tower produces
Object, and good magnetic oxide protective film is formed in metal surface, passivating metallic surfaces effectively delay the corrosion of caustic wash tower.
4) butter inhibitor further includes alkylhydroxyoximate, is had in alkylhydroxyoximate molecular structure containing lone pair electrons
Oxygen and nitrogen, and position is close to each other, which enables it to generate stable chelate with metal ion-chelant, prevent metal from
The catalytic action of son, and then inhibit the formation of cross-linked polymer.
5) above-mentioned butter inhibitor can dissolve the generated butter of dispersion, and comprehensive ethene suppressing produces alkaline cleaning procedure
The generation of middle butter guarantees that caustic wash tower operation is smooth, improves alkali cleaning effect, improve Ethylene Plant Efficiency.
6) above-mentioned butter inhibitor may be uniformly dispersed in the material of caustic wash tower because of its physical property feature, make the suppression of butter
Effect processed reaches best；The various polymerization reactions for generating butter can be effectively controlled in multi-component formula system, effectively inhibition alkali cleaning
The generation of butter in tower, extends the cycle of operation of caustic wash tower, reduces the discharge of spent lye and the consumption of fresh lye, reduces because of Huang
Environmental pollution caused by oil discharge；Meanwhile above-mentioned butter inhibitor is safe and non-toxic, environmentally protective, does not have to environment and downstream product
There is pollution, and using simplicity, does not need to be transformed existing equipment, synergistic effect is strong between each component, and dosage is few, and effect is good,
Cost performance is high.Therefore, above-mentioned butter inhibitor can bring significant economic benefit and social benefit for ethylene production.
The preparation method of the butter inhibitor of one embodiment is one of preparation method of above-mentioned butter inhibitor,
The preparation method of the butter inhibitor comprising steps of
Step S100: according to mass fraction meter, 20 parts~35 parts of acetoacetic ester, 15 parts~25 parts of nitrogen oxygen is free
Base, 1 part~10 parts of polycarboxylate, 5 parts~15 parts of polyethenoxy ether class compound and the mixing of 15 parts~40 parts of diluent,
Obtain butter inhibitor.
Wherein, step S100 specifically: 1 part~10 parts of polycarboxylate and 15 parts~40 parts of diluent are added to appearance
In device, is stirred with the revolving speed of 200r/min~600r/min to being completely dissolved under conditions of 50 DEG C~60 DEG C, be then added 20
Part~35 parts of acetoacetic ester, 15 parts~25 parts of NO free radical and 5 parts~15 parts of polyethenoxy ether class compound, are stirred
0.5h~3h is mixed, cooling, filtering obtains butter inhibitor.
Further, the general structure of acetoacetic ester is CH3COCH2COOCnHm, wherein n is any whole in 1~10
Number, m are the arbitrary integer in 3~21.Further, the mass fraction of acetoacetic ester is 22 parts~30 parts.
Specifically, acetoacetic ester is selected from methyl acetoacetate, ethyl acetoacetate, propyl acetoacetate, acetoacetate
At least one of butyl ester and acetoacetic acid allyl ester.More specifically, acetoacetic ester is selected from methyl acetoacetate and acetyl second
At least one of acetoacetic ester.
Further, the mass fraction of NO free radical is 18 parts~22 parts.Specifically, NO free radical is piperidines nitrogen
Oxygen radical.More specifically, NO free radical be selected from 2,2,6,6- tetramethyl piperidine -1- oxygen radicals, 4- hydroxyl -2,2,6,6-
At least one of tetramethyl piperidine -1- oxygen radical and 4- oxygen -2,2,6,6- tetramethyl piperidine -1- oxygen radical.
Further, the mass fraction of polycarboxylate is 3 parts~8 parts.Specifically, polycarboxylate be selected from Sodium Polyacrylate and
At least one of sodium polymethacrylate.More specifically, the number-average molecular weight of polycarboxylate is 1000~5000.Implement one
In example, polycarboxylate is the Sodium Polyacrylate that number-average molecular weight is 2000~3000.
Further, the mass fraction of polyethenoxy ether class compound is 8 parts~12 parts.Specifically, polyethenoxy ether class
It is stearic that compound is selected from dodecyl phenol polyethenoxy ether, sorbitan monooleate polyoxyethylene ether, anhydrous sorbitol list
At least one of acid ester polyoxyethylene ether, ethoxylated dodecyl alcohol and lauric alcohol polyoxyethylene ether.
Further, the number-average molecular weight of polyethenoxy ether class compound is 1000~5000.Further, polyoxy second
Alkene ether compound is selected from the sorbitan monooleate polyoxyethylene ether that number-average molecular weight is 2000~3000 and number is divided equally
At least one of the lauric alcohol polyoxyethylene ether that son amount is 2000~3000.
Further, the mass fraction of diluent is 20 parts~35 parts.Specifically, diluent is water.More specifically, dilution
Agent is deionized water.
It should be noted that further including the hydroxyl amine chemical combination that joined mass fraction and be 20 parts~35 parts in step S100
Object.Further, the mass fraction of hydroxyl amine compound is 22 parts~30 parts.Specifically, the structure of hydroxyl amine compound
General formula is R1(R2)N-(CH2)k- OH, wherein R1And R2It is separately former selected from hydrogen, the alkyl that carbon atom number is 1~10 and carbon
One of the aralkyl that subnumber is 7~15, k are the arbitrary integer in 0~8.
Further, hydroxyl amine compound is selected from N, N- diethyl hydroxylamine, N- isopropylhydroxyla, N, N- dibenzyl hydroxyl
At least one of amine, monoethanolamine, triethanolamine and triisopropanolamine.Further, hydroxyl amine compound is selected from N,
At least one of N- diethyl hydroxylamine, N- isopropylhydroxyla and monoethanolamine.
It should be noted that further including the dialkyl group ketoxime that joined mass fraction and be 1 part~15 parts in step S100.Into
One step, the mass fraction of dialkyl group ketoxime is 5 parts~10 parts.Specifically, dialkyl group ketoxime is selected from dimethyl ketone oxime, methyl second
At least one of base ketoxime, methyl-propyl ketoxime and methyl isobutyl ketoxime.
It should be noted that further including the alkylhydroxyoximate that joined mass fraction and be 1 part~15 parts in step S100.
Further, the mass fraction of alkylhydroxyoximate is 5 parts~10 parts.Specifically, the general structure of alkylhydroxyoximate is
RCONHONa, wherein R is the alkyl that carbon atom number is 4~9.More specifically, the alkylhydroxyoximate is selected from octyl hydroximic acid
At least one of sodium, cyclohexyl methyl sodium alkyl hydroxamate and nonyl sodium alkyl hydroxamate.
Preparation method is simple for above-mentioned butter inhibitor, is suitable for industrialized production.
Butter inhibitor made from the preparation method of above-mentioned butter inhibitor or above-mentioned butter inhibitor is in preparation second
Application in alkene.Specifically, butter made from the preparation method of above-mentioned butter inhibitor or above-mentioned butter inhibitor inhibits
Application of the agent in ethylene cracker caustic wash tower.Wherein, by butter inhibitor ethylene cracker caustic wash tower it is strong, in and it is weak
It is injected at alkali section pipeloop, on the basis of ethylene, propylene and total butadiene content, the butter inhibitor concentration after injection is
10ppm~500ppm.Further, butter inhibitor concentration is 20ppm~100ppm.
The following are specific embodiment parts:
Alkylhydroxyoximate, polycarboxylate and diluent are added in container, warming while stirring to T is completely dissolved
Acetoacetic ester, NO free radical, hydroxyl amine compound, dialkyl group ketoxime and polyethenoxy ether class compound are added afterwards to carry out
Stirring, the revolving speed of stirring are X, and the time of stirring is Y, and cooling, filtering obtains butter inhibitor.Wherein, alkylhydroxyoximate,
Polycarboxylate, diluent, acetoacetic ester, NO free radical, hydroxyl amine compound, dialkyl group ketoxime and polyethenoxy ether class
The mass fraction of compound, the value of T, X and Y are as shown in table 1.
Table 1
Test:
1) butter inhibitor that Examples 1 to 9 is prepared is respectively applied to ethylene cracker caustic wash tower simulation dress
It sets, wherein cracking stock is naphtha, and ethylene, propylene and butadiene total recovery are 48.6% in cracking gas, and simulation caustic wash tower is strong
Alkali section lye (NaOH solution) concentration is 8%, and middle alkali section lye (NaOH solution) concentration is 5%, and (NaOH is molten for weak base section lye
Liquid) concentration is 2%, using electromagnetic pump by butter inhibitor it is strong, in, be continuously injected into weak base pipeloop, butter inhibitor
Implantation concentration is 100ppm, and the chemistry consumption of each alkali section lye is tested in device operation using the test method of GB8978-1996 afterwards for 24 hours
Oxygen amount (COD) value, and butter content is measured, it the results are shown in Table 2, wherein blank is that the comparative test of butter inhibitor is not added.
Table 2
From table 2 it can be seen that compared with blank, using each alkali section lye of butter inhibitor made from Examples 1 to 9
COD value and butter content are substantially reduced, and illustrate that butter inhibitor made from Examples 1 to 9 being capable of obvious ethene suppressing production alkali
The generation of butter during washing inhibits elaioleucite coalescence, reduces COD value；In addition, butter inhibitor made from Examples 1 to 9 can also
Enough improve oil reservoir color.
In addition, compared with embodiment 7~9, using the COD of each alkali section lye of butter inhibitor made from Examples 1 to 6
It is worth lower, butter content is lower, illustrates that the addition of hydroxyl amine compound, dialkyl group ketoxime and alkylhydroxyoximate obviously helps
In the inhibitory effect of butter inhibitor, further explain hydroxyl amine compound, dialkyl group ketoxime and alkylhydroxyoximate with
Acetoacetic ester, NO free radical have significant synergistic effect.
2) butter inhibitor made from embodiment 1, embodiment 2 and embodiment 8 is respectively applied to ethylene unit alkaline washing tower
Simulator, method add dosage to inject butter inhibitor with 1) by shown in table 3, butter inhibitor is not added and Jilin is added
Petrochemical industry is comparison at the LD-15 butter inhibitor that profit auxiliary chemicals Co., Ltd develops, and the results are shown in Table 3.Wherein, inhibiting rate=
(1-m1/m2) × 100%, m1 is that the COD value measured after butter inhibitor is added in formula, and m2 is that Huang is not added under similarity condition
The COD value obtained when oily inhibitor；Alternatively, m1 is that the butter amount measured after butter inhibitor is added, m2 is similarity condition
Under the butter amount that obtains when butter inhibitor is not added.
Table 3
From table 3 it can be seen that under identical plus dosage, Huang of the commercially available butter inhibitor LD-15 to each alkali section of caustic washing system
Oily inhibitory effect can not show a candle to butter inhibitor made from embodiment 1, embodiment 2 and embodiment 8；When butter inhibitory effect is suitable
When, butter inhibitor made from embodiment 1, embodiment 2 and embodiment 8 plus dosage be much smaller than commercially available butter inhibitor LD-15.
Therefore, butter inhibitor made from embodiment 1, embodiment 2 and embodiment 8 has good butter to ethylene production alkaline cleaning procedure
Inhibitory effect significantly promotes to make to improving alkali cleaning effect, raising Ethylene Plant Efficiency, guaranteeing that caustic wash tower operation smoothness has
With.
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (10)
1. a kind of butter inhibitor, which is characterized in that according to mass fraction meter, including
Wherein, the general structure of the acetoacetic ester is CH3COCH2COOCnHm, wherein n is the arbitrary integer in 1~10, m
For the arbitrary integer in 3~21；The NO free radical is piperidine nitroxide free-radical.
2. butter inhibitor according to claim 1, which is characterized in that the acetoacetic ester is selected from acetoacetate first
At least one of ester, ethyl acetoacetate, propyl acetoacetate, butyl-acetoacetate and acetoacetic acid allyl ester.
3. butter inhibitor according to claim 1, which is characterized in that the NO free radical is selected from 2,2,6,6- tetramethyls
Phenylpiperidines -1- oxygen radical, 4- hydroxyl -2,2,6,6- tetramethyl piperidine -1- oxygen radical and 4- oxygen -2,2,6,6- tetramethyl piperazine
At least one of pyridine -1- oxygen radical.
4. butter inhibitor according to claim 1, which is characterized in that the polycarboxylate is selected from Sodium Polyacrylate and gathers
At least one of Sodium methacrylate.
5. butter inhibitor according to claim 1, which is characterized in that the polyethenoxy ether class compound is selected from 12
Alkyl phenol polyoxyethylene ether, sorbitan monooleate polyoxyethylene ether, sorbitan monostearate polyoxyethylene ether,
At least one of ethoxylated dodecyl alcohol and lauric alcohol polyoxyethylene ether.
6. butter inhibitor according to claim 1, which is characterized in that further include the hydroxyl that mass fraction is 20 parts~35 parts
Base aminated compounds, the general structure of the hydroxyl amine compound are R1(R2)N-(CH2)k- OH, wherein R1And R2It is only respectively
On the spot being selected from hydrogen, the alkyl that carbon atom number is 1~10 and carbon atom number is one of 7~15 aralkyl, and k is in 0~8
Arbitrary integer.
7. butter inhibitor according to claim 1, which is characterized in that further include two that mass fraction is 1 part~15 parts
Alkyl ketoxime.
8. butter inhibitor according to claim 1, which is characterized in that further include the alkane that mass fraction is 1 part~15 parts
Base hydroximic acid salt, the general structure of the alkylhydroxyoximate are RCONHONa, wherein R is the alkyl that carbon atom number is 4~9.
9. a kind of preparation method of butter inhibitor, which is characterized in that comprising steps of
According to mass fraction meter, by 20 parts~35 parts of acetoacetic ester, 15 parts~25 parts of NO free radical, 1 part~10 parts
Polycarboxylate, 5 parts~15 parts of polyethenoxy ether class compound and 15 parts~40 parts diluent mixing, obtain butter inhibition
Agent, wherein the general structure of the acetoacetic ester is CH3COCH2COOCnHm, wherein n is the arbitrary integer in 1~10, m
For the arbitrary integer in 3~21；The NO free radical is piperidine nitroxide free-radical.
10. the system of butter inhibitor described in claim 1~8 any one or butter inhibitor as claimed in claim 9
Butter inhibitor made from Preparation Method is preparing the application in ethylene.
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| CN201910131199.4A CN109879715B (en) | 2019-02-22 | 2019-02-22 | Butter inhibitor and preparation method and application thereof |
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| CN112209798A (en) * | 2019-07-10 | 2021-01-12 | 中国石油化工股份有限公司 | Butter inhibitor composition for methanol-to-olefin caustic tower and method for inhibiting butter generation |
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