CN104130151A - Method for preparing fluorocarbon alkylamide through fixed bed catalytic reaction - Google Patents
Method for preparing fluorocarbon alkylamide through fixed bed catalytic reaction Download PDFInfo
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- CN104130151A CN104130151A CN201410336035.2A CN201410336035A CN104130151A CN 104130151 A CN104130151 A CN 104130151A CN 201410336035 A CN201410336035 A CN 201410336035A CN 104130151 A CN104130151 A CN 104130151A
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- acid amides
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Abstract
The invention relates to a method for preparing fluorocarbon alkylamide through a fixed bed catalytic reaction. According to the method, perfluorocarboxylic acid and polyene polyamine are adopted as raw materials; polyene polyamine is added into a preheating kettle; perfluorocarboxylic acid with a determined quantity is slowly added; the temperature is maintained at 110-160 DEG C; preheated liquid is pumped into a fixed bed reactor loaded with a catalyst; and a reaction material flown from the fixed bed reactor is pumped into the preheating kettle by using a reflux pump. The material is circulated for 2-4h in the reaction system. During the reaction process, a vacuum degree of 0MPa to -0.4MPa is maintained, and water produced by the reaction is pumped out. As a result of an ultraviolet spectrophotometry sample test, a product content is higher than 98%, such that the product is qualified. The obtained product is N-aminoethyl(or diethyl diamine)-perfluoroalkyl amide. The method provided by the invention has the characteristics of simple process, no solvent, stable operation control, short reaction time, high single-kettle yield, high product purity, low three-waste pollution, environment-friendliness, easy industrialization, and the like.
Description
Technical field
The present invention relates to the preparation method of a class fluorocarbon surfactant, be mainly used in preventing the corrosion of corrosive medium to hardware in the exploitation of high temperature oil gas field and petroleum refining process.Fluorocarbon surfactant also has foam performance, can be applicable to fire foam field and Natural gas extraction with in foaming acid.Especially the present invention relates to utilize fixed bed catalyst to prepare the method for N-aminoethyl (or diethyl diamino)-perfluoroalkyl amide compound.
Background technology
Along with oilfield exploitation continue carry out, oil well overdraft reduces, yield reducation will increase production by the water filling supercharging displacement of reservoir oil and acidizing treatment.Such well stimulation causes water content in crude oil and corrosive medium to increase substantially.In water due to oil well produced liquid, contain Ca
2+, Mg
2+, O
2, CO
2, SO
4 2-, C1
-, HCO
3 -, H
2the corrosive mediums such as S, SRB (sulphate reducing bacteria), can cause heavy corrosion to equipment such as the adopting of crude oil, collection, defeated, refinings, cause environmental pollution and financial loss.Seek effectively to prevent the technology of Produced Liquid to equipment corrosion, become and guaranteed the normal Focal point and difficult point of producing in oil field.Meanwhile, the high temperature acidified volume increase field in oil field, the high concentrated acid of use (being generally mud acid) has heavy corrosion to equipment, must suppress corrosion with efficient heatproof inhibiter.And conventional inhibiter is as alkynol, aldehydes and alkane benzene pyridines, conventionally there is the shortcomings such as large usage quantity, poorly water-soluble, corrosion inhibition rate be low.General hydrocarbon amides, tetrahydroglyoxaline component inhibiter be meeting decomposition failure in high temperature (more than 120 ℃), high density acid solution, has limited its use in oil mining.Fluorine carboxamide compound, owing to containing in molecular structure compared with strong electronegativity and hydrophobic carbon-fluorine bond, makes it have in actual applications good surfactivity, higher heat resistance, good corrosion inhibition.
Acid amide type non-ion fluorin carbon surface active agent synthetic is mainly that to adopt fatty acid process, take perfluoroalkyl acid and diethanolamine be main raw material, because its environmental compatibility is strong, difficult and charged group generation coagulation, by the general numerous areas such as suds-stabilizing agent, washing composition, static inhibitor that are applied to.This kind of building-up process is mainly divided into two steps, and the first step be take esterification as main, successive reaction 4h left and right at the temperature of 160 ℃ of left and right, and the condition of building-up reactions is harsher.In addition, adopting diethanolamine is to contain nitrosamines carcinogens in the synthetic series product of main raw material, to environment and healthy unfavorable, is not suitable for industrial applications widely.
CN1743062A (CN200510041066.6) discloses a kind of fluorine-carbon sufactant, to take the fluorine-carbon sufactant of the novel hydrophilic flexible spacer that hydrophilic monoesters propylene dichloride is spacer group, chemistry N by name, N, N ', N ' tetramethyl-one N, N ' a pair of [(perfluoroalkyl sulfoamido) alkyl] one 2-monoesters base, one propane-diammonium.This tensio-active agent is by perfluoroalkyl sulfonyl fluoride and N, N-dimethyl 1,2-quadrol or N, N-dimethyl 1,3-propylene diamine reacts to obtain intermediate product N-[(dimethylamino) alkyl] perfluoroalkyl sulphonamide, then carry out quaterisation with monoesters propylene dichloride and product.But in the method preparation process, have severe corrosive side reaction to occur, equipment material is had relatively high expectations, environmental pollution is larger.
CN102766064A discloses the preparation method of a kind of fluorine carbon pore forming material N-(2-hydroxypropyl) perfluor decoylamide, take α-amino isopropyl alcohol and Perfluorocaprylic Acid as raw material, synthesize in two steps N-(2-hydroxypropyl) perfluor decoylamide, synthesize and take NaOH as catalyzer, complete in two steps 13 hours reaction times.Long reaction time of the present invention, catalyzer is not easily separated, and product purity is influenced larger.
CN102766065A discloses a kind of synthetic method of fluorocarbon surfactant N-dihydroxy ethyl perfluor decoylamide.The method is that to take Perfluorocaprylic Acid and diethanolamine be raw material; sodium hydroxide is catalyzer; utilize amidate action to prepare N-dihydroxy ethyl perfluor decoylamide; step is: Perfluorocaprylic Acid and diethanolamine are mixed with mol ratio 1:1.4～2.2; under nitrogen protection, be heated to 120～200 ℃ of reactions 2～8 hours, do not stop to stir, be cooled to add after 40～100 ℃ 0.1～1.0% catalyzer sodium hydroxide; continue reaction 2～8 hours, cooling drying obtains product N-dihydroxy ethyl perfluor decoylamide.There is long reaction time in the present invention, catalyzer is not easily separated, larger on product purity impact.
Summary of the invention
For overcome the long reaction time, the catalyzer that in existing fluorine carbon alkylamide preparation method, exist not easily separated, on product purity impact the problem such as large or reaction process punching material easy to foaming, solvent recuperation and environmental pollution, the present invention proposes that a kind of to take the molecular sieve carried phospho-wolframic acid of activated alumina be catalyzer, utilize fixed bed catalyst to prepare the method for fluorine carbon alkylamide.
Technical solution of the present invention is as follows: a kind of fixed bed catalyst is prepared the method for fluorine carbon alkylamide, comprise that step is as follows: (1) calculates weighing in 1:1.02～1.05 in molar ratio by perfluorocarboxylic acid and polyamines polyene raw material, first polyamines polyene is joined with in the preheating reactor that stirs and heat, (2) in preheating reactor, polyamines polyene is heated to after 30～35 ℃, under stirring state, slowly add quantitative perfluorocarboxylic acid, add rear intensification, between 110 ℃～160 ℃, be incubated 30～60min, with fixed bed fresh feed pump by the preheating liquid pump in preheating reactor enter to fill catalyzer can the fixed-bed reactor of heating and thermal insulation in, with reflux pump, the reaction mass flowing out from fixed-bed reactor is pumped into preheating reactor again, (3) fixed-bed reactor top is provided with condenser and vacuum unit, keep 0～-0.4MPa vacuum tightness, from reactive system, extract generation water, reaction mass from preheating reactor to fixed-bed reactor, and then circulate 2～4 hours in preheating reactor, utilize ultraviolet spectrophotometry sampling and testing product content to be greater than 98%, it is qualified to be, all reactants are returned in preheating reactor, products obtained therefrom is N-aminoethyl (or diethyl diamino)-perfluoroalkyl acid amides.
The described perfluorocarboxylic acid of step (1) is one of perfluor valeric acid, perfluor caproic acid, perfluoro-heptanoic acid, Perfluorocaprylic Acid, perfluoro-pelargonic acid, perfluoro decanoate; Polyamines polyene is one of diethylenetriamine, triethylene tetramine.
The described catalyzer of step (2) is activated alumina load phosphotungstic acid catalyst, and its consumption is for dropping into 1.5～4% of reactant quality summation.
Described N-aminoethyl (or diethyl diamino)-perfluoroalkyl acid amides of step (3) is one of N-aminoethyl-perfluoro butyl acid amides, N-aminoethyl-perfluor amyl group acid amides, N-aminoethyl-perfluoro hexyl acid amides, N-aminoethyl-perfluor heptyl acid amides, N-aminoethyl-perfluoro capryl acid amides, N-aminoethyl-perfluor nonyl acid amides, N-diethyl diamino-perfluor heptyl acid amides, N-diethyl diamino-perfluoro capryl acid amides.
The present invention adopts the molecular sieve carried phospho-wolframic acid solid catalyst of activated alumina and fixed-bed tube reactor, compare with original preparation technology, do not use that solvent, its technique are simple, operation control stable, the reaction times is short, single-autoclave yield rate is high, purity is compared with various features such as high, three-waste pollution is little, environmentally friendly, easy industrialization.
Embodiment
By embodiment, further illustrating the present invention, is not limitation of the invention.
Embodiment 1:
In thermometer, agitator and manometric 500ml stainless steel cauldron are housed, add 100g diethylenetriamine, be heated to 30 ℃, after being warmed up to 130 ℃ after adding 252g perfluor valeric acid to stir, be incubated 30min, with fixed bed fresh feed pump, preheating liquid pump is entered to fill in the fixed-bed reactor of 7g activated alumina load phosphotungstic acid catalyst, with reflux pump, will flow out material from fixed bed again and pump into still preheater, the flow velocity of pump is 30ml/min simultaneously.Give fixed bed 0～-0.4MPa vacuum tightness simultaneously, extract generation water.Circulate 2.5 hours, sampling and testing, obtains N-aminoethyl-perfluoro butyl acid amides product 334.6g, content 98.4%, and yield is 95.6%.This product infrared signature is at 1700CM
-1place is the carbonyl charateristic avsorption band of acid amides, and occurs 3300CM
-1nH
2strong absorption peak, 2950CM
-1cH
2-CH
2strong absorption peak, 1200CM
-1and 1150CM
-1the CF at place
3-CF
2strong absorption peak.
Embodiment 2:
In thermometer, agitator and manometric 500ml stainless steel cauldron are housed, add 100g diethylenetriamine, be heated to 30 ℃, after being warmed up to 132 ℃ after adding 299g perfluor caproic acid to stir, be incubated 30min, with fixed bed fresh feed pump, preheating liquid pump is entered to fill in the fixed-bed reactor of 8g activated alumina load phosphotungstic acid catalyst, with reflux pump, will flow out material from fixed bed again and pump into still preheater, the flow velocity of pump is 30ml/min simultaneously.Give fixed bed 0～-0.4MPa vacuum tightness simultaneously, extract generation water.Circulate 3 hours, sampling and testing, obtains N-aminoethyl-perfluor amyl group acid amides product 364.9g, content 99.1%, and yield is 96.7%.
Embodiment 3:
In thermometer, agitator and manometric 500ml stainless steel cauldron are housed, add 100g diethylenetriamine, be heated to 34 ℃, after being warmed up to 130 ℃ after adding 349g perfluoro-heptanoic acid to stir, be incubated 30min, with fixed bed fresh feed pump, preheating liquid pump is entered to fill in the fixed-bed reactor of 9g activated alumina load phosphotungstic acid catalyst, with reflux pump, will flow out material from fixed bed again and pump into still preheater, the flow velocity of pump is 30ml/min simultaneously.Give fixed bed 0～-0.4MPa vacuum tightness simultaneously, extract generation water.Circulate 4 hours, sampling and testing, obtains N-aminoethyl-perfluoro hexyl acid amides product 409.1g, content 98.5%, and yield is 95.8%.
Embodiment 4:
In thermometer, agitator and manometric 500ml stainless steel cauldron are housed, add 100g diethylenetriamine, be heated to 30 ℃, after being warmed up to 131 ℃ after adding 395g Perfluorocaprylic Acid to stir, be incubated 30min, with fixed bed fresh feed pump, preheating liquid pump is entered to fill in the fixed-bed reactor of 10g activated alumina load phosphotungstic acid catalyst, with reflux pump, will flow out material from fixed bed again and pump into still preheater, the flow velocity of pump is 30ml/min simultaneously.Give fixed bed 0～-0.4MPa vacuum tightness simultaneously, extract generation water.Circulate 4 hours, sampling and testing, obtains N-aminoethyl-perfluor heptyl acid amides product 459.87g, content 99.4%, and yield is 97.1%.
Embodiment 5:
In thermometer, agitator and manometric 500ml stainless steel cauldron are housed, add 90g diethylenetriamine, be heated to 30 ℃, after being warmed up to 148 ℃ after adding 397.6g perfluoro-pelargonic acid to stir, be incubated 30min, with fixed bed fresh feed pump, preheating liquid pump is entered to fill in the fixed-bed reactor of 10g activated alumina load phosphotungstic acid catalyst, with reflux pump, will flow out material from fixed bed again and pump into still preheater, the flow velocity of pump is 30ml/min simultaneously.Give fixed bed 0～-0.4MPa vacuum tightness simultaneously, extract generation water.Circulate 4 hours, sampling and testing, obtains N-aminoethyl-perfluoro capryl acid amides product 441.86g, content 98.8%, and yield is 96.2%.
Embodiment 6:
In thermometer, agitator and manometric 500ml stainless steel cauldron are housed, add 90g diethylenetriamine, be heated to 32 ℃, after being warmed up to 160 ℃ after adding 440.5g perfluoro decanoate to stir, be incubated 30min, with fixed bed fresh feed pump, preheating liquid pump is entered to fill in the fixed-bed reactor of 10.6g activated alumina load phosphotungstic acid catalyst, with reflux pump, will flow out material from fixed bed again and pump into still preheater, the flow velocity of pump is 30ml/min simultaneously.Give fixed bed 0～-0.4MPa vacuum tightness simultaneously, extract generation water.Circulate 4 hours, sampling and testing, obtains N-aminoethyl-perfluor nonyl acid amides product 478.1g, content 98.1%, and yield is 95.2%.
Embodiment 7:
In thermometer, agitator and manometric 500ml stainless steel cauldron are housed, add 100g triethylene tetramine, be heated to 35 ℃, after being warmed up to 150 ℃ after adding 277.6g Perfluorocaprylic Acid to stir, be incubated 30min, with fixed bed fresh feed pump, preheating liquid pump is entered to fill in the fixed-bed reactor of 7.6g activated alumina load phosphotungstic acid catalyst, with reflux pump, will flow out material from fixed bed again and pump into still preheater, the flow velocity of pump is 30ml/min simultaneously.Give fixed bed 0～-0.4MPa vacuum tightness simultaneously, extract generation water.Circulate 4 hours, sampling and testing, obtains N-diethyl diamino-perfluor heptyl acid amides product 315.27g, content 98%, and yield is 94.8%.
Embodiment 8:
In thermometer, agitator and manometric 500ml stainless steel cauldron are housed, add 100g triethylene tetramine, be heated to 35 ℃, after being warmed up to 160 ℃ after adding 310.9g perfluoro-pelargonic acid to stir, be incubated 30min, with fixed bed fresh feed pump, preheating liquid pump is entered to fill in the fixed-bed reactor of 8.2g activated alumina load phosphotungstic acid catalyst, with reflux pump, will flow out material from fixed bed again and pump into still preheater, the flow velocity of pump is 30ml/min simultaneously.Give fixed bed 0～-0.4MPa vacuum tightness simultaneously, extract generation water.Circulate 4 hours, sampling and testing, obtains N-diethyl diamino-perfluoro capryl acid amides product 354.24g, content 98.9%, and yield is 96.3%.
Claims (4)
1. a fixed bed catalyst is prepared the method for fluorine carbon alkylamide, it is characterized in that: comprise that step is as follows: (1) calculates weighing in 1:1.02～1.05 in molar ratio by perfluorocarboxylic acid and polyamines polyene raw material, first polyamines polyene is joined with in the preheating reactor that stirs and heat, (2) in preheating reactor, polyamines polyene is heated to after 30～35 ℃, under stirring state, slowly add quantitative perfluorocarboxylic acid, add rear intensification, between 110 ℃～160 ℃, be incubated 30～60min, with fixed bed fresh feed pump by the preheating liquid pump in preheating reactor enter to fill catalyzer can the fixed-bed reactor of heating and thermal insulation in, with reflux pump, the reaction mass flowing out from fixed-bed reactor is pumped into preheating reactor again, (3) fixed-bed reactor top is provided with condenser and vacuum unit, keep 0～-0.4MPa vacuum tightness, from reactive system, extract generation water, reaction mass from preheating reactor to fixed-bed reactor, and then circulate 2～4 hours in preheating reactor, utilize ultraviolet spectrophotometry sampling and testing product content to be greater than 98%, it is qualified to be, all reactants are returned in preheating reactor, products obtained therefrom is N-aminoethyl (or diethyl diamino)-perfluoroalkyl acid amides.
2. the preparation method of fluorine carbon alkylamide according to claim 1, is characterized in that, the described perfluorocarboxylic acid of step (1) is one of perfluor valeric acid, perfluor caproic acid, perfluoro-heptanoic acid, Perfluorocaprylic Acid, perfluoro-pelargonic acid, perfluoro decanoate; Polyamines polyene is one of diethylenetriamine, triethylene tetramine.
3. the preparation method of fluorine carbon alkylamide according to claim 1, is characterized in that, the described catalyzer of step (2) is activated alumina load phosphotungstic acid catalyst, and its consumption is for dropping into reactant quality summation 1.5～4%.
4. the preparation method of fluorine carbon alkylamide according to claim 1, it is characterized in that, described N-aminoethyl (or diethyl diamino)-perfluoroalkyl acid amides of step (3) is one of N-aminoethyl-perfluoro butyl acid amides, N-aminoethyl-perfluor amyl group acid amides, N-aminoethyl-perfluoro hexyl acid amides, N-aminoethyl-perfluor heptyl acid amides, N-aminoethyl-perfluoro capryl acid amides, N-aminoethyl-perfluor nonyl acid amides, N-diethyl diamino-perfluor heptyl acid amides, N-diethyl diamino-perfluoro capryl acid amides.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106278922A (en) * | 2016-08-15 | 2017-01-04 | 广州天赐高新材料股份有限公司 | A kind of preparation method of fatty acid amide propyl tertiary amine |
| CN110452160A (en) * | 2019-09-26 | 2019-11-15 | 江苏欣舟化工科技有限公司 | The preparation method of bis- (2,2,6,6- tetramethyl -4- the piperidyl) -1,3- benzenedicarboxamides of N, N ' - |
| CN112341364A (en) * | 2020-09-29 | 2021-02-09 | 陈力群 | Preparation method and application of surfactant |
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| CN102766064A (en) * | 2012-08-15 | 2012-11-07 | 中国石油大学(华东) | Preparation method of fluorocarbon foaming agent N-(2-hydroxy propyl) perfluorocaprylamide |
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2014
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| CN101891645A (en) * | 2010-07-27 | 2010-11-24 | 陕西科技大学 | Method for preparing salicylamide |
| CN102766064A (en) * | 2012-08-15 | 2012-11-07 | 中国石油大学(华东) | Preparation method of fluorocarbon foaming agent N-(2-hydroxy propyl) perfluorocaprylamide |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106278922A (en) * | 2016-08-15 | 2017-01-04 | 广州天赐高新材料股份有限公司 | A kind of preparation method of fatty acid amide propyl tertiary amine |
| CN110452160A (en) * | 2019-09-26 | 2019-11-15 | 江苏欣舟化工科技有限公司 | The preparation method of bis- (2,2,6,6- tetramethyl -4- the piperidyl) -1,3- benzenedicarboxamides of N, N ' - |
| CN112341364A (en) * | 2020-09-29 | 2021-02-09 | 陈力群 | Preparation method and application of surfactant |
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