CN102153491A - Synthesis method of long-chain alkyl dihydroxyethyl amine oxide - Google Patents
Synthesis method of long-chain alkyl dihydroxyethyl amine oxide Download PDFInfo
- Publication number
- CN102153491A CN102153491A CN2011100226555A CN201110022655A CN102153491A CN 102153491 A CN102153491 A CN 102153491A CN 2011100226555 A CN2011100226555 A CN 2011100226555A CN 201110022655 A CN201110022655 A CN 201110022655A CN 102153491 A CN102153491 A CN 102153491A
- Authority
- CN
- China
- Prior art keywords
- chain alkyl
- amine
- raw material
- amine oxide
- long
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
The invention discloses a method for synthesizing long-chain alkyl dihydroxyethyl amine oxide by oxidizing long-chain alkyl dihydroxyethyl amine with hydrogen peroxide, which is characterized in that the conversion rate of the raw material tertiary amine is controlled at 90-95%, and the unconverted raw material tertiary amine is used as a corrosion inhibitor for enhancing the corrosion inhibition function of the surfactant. The method comprises the following steps: (1) mixing the raw material long-chain dihydroxyethyl amine and deionized water to form an emulsion, and heating to 60-80 DEG C; (2) slowly and dropwisely adding a hydrogen peroxide solution to oxidize the long-chain alkyl dihydroxyethyl amine, and after finishing adding the hydrogen peroxide solution, keeping the temperature to react for 3-4 hours; and (3) when the conversion rate of the raw material tertiary amine reaches 90-95%, adding sodium hypophosphite to decompose residual hydrogen peroxide and regulate the concentration of amine oxide in the solution to 40%. When the long-chain alkyl dihydroxyethyl amine oxide is used as a drag reducer for a circulating water system of 5-60 DEG C, and added into the circulating water system for evaluation in the effective concentration of 0.2-1.0kg/m<3>, the drag reduction rate is up to 50-65%, and the corrosion inhibition efficiency is up to 98-99%. The synthesis method of long-chain alkyl dihydroxyethyl amine oxide has the advantage of high utilization ratio of raw material, and is simple to implement. The product synthesized by the method disclosed by the invention has the characteristic of wide range of applicable temperature and has the function of corrosion inhibition for common metal pipelines when being used as an energy-saving drag reducer for a circulating water system.
Description
Technical field
The present invention relates to a kind of chain alkyl dihydroxy ethyl amine oxide synthetic method and application, particularly a kind of synthetic method of the chain alkyl dihydroxy ethyl amine oxide with corrosion inhibitive function and as the application of drag-reduction energy-saving agent.
Background technology
Soluble in water and the polar organic solvent of long-chain alkyl amine oxide, it is a kind of weak cation type amphoterics, its aqueous solution is cationic under acidic conditions, be nonionic under alkaline condition, has good thickening, antistatic, soft, foam enhancing, detergency ability; Also have sterilization, lime soap dispersing power, and biological degradability is good; Long-chain alkyl amine oxide character gentleness, pungency are low, can reduce the pungency of anion surfactant in the washing composition effectively, belong to the environment-friendly type daily chemical products; Also can be used in plastic working, the textile printing and dyeing industry as the static inhibitor recipe ingredient; Also can be used as the agent of industrial circulating water drag-reduction energy-saving uses.
Commercial long-chain alkyl amine oxide mainly contains long chain alkyl dimethyl amine oxide, chain alkyl dihydroxy ethyl amine oxide and chain alkyl amido propyl dimethyl oxidation amine, and its molecular structural formula is as follows:
The applied research of long-chain alkyl amine oxide is since the sixties in 20th century, J.Am.oil chemists Soc.1963 o. 11th, describe the reaction of long chain alkyl dimethyl tertiary amine and hydrogen peroxide among the 628-631 in detail, long chain alkyl dimethyl tertiary amine and excessive 10% 35% aqueous hydrogen peroxide solution are 75 ℃ of reactions down in reaction process, during reaction add water continuously to keep the flowability of mixture, reacted 3-4 hour, the tertiary amine transformation efficiency is near 100%, and the remaining hydrogen peroxide in reaction back is removed by adding S-WAT.Present industrial long-chain alkyl amine oxide is made with hydrogen peroxide oxidation by the corresponding long chain alkyl tertiary amine exactly.
Chemical equation by long-chain alkyl tertiary amine synthesizing long-chain alkyl amine oxide is as follows:
In the formula, R1 is the chain alkyl of C8-C22, and representational have lauryl, palmityl, hard ester group, cocoyl, oil base, tallow and a soya-bean oil base; R2, R3 are methyl, ethyl, hydroxyethyl or hydroxypropyl.Hydrogen peroxide is a 35%-70% solution; Oxidation solvent is water, methyl alcohol, ethanol, Virahol or benzene kind solvent.
The patent of long-chain alkyl amine oxide synthetic method is a lot, is the improvement of carrying out at oxidation solvent, temperature, catalyzer or additive mostly, to improve the quality and to reduce hydrogen peroxide consumption and satisfy the detergents and cosmetic Application for Field.For example, Chinese patent CN1137940 (1996-12-18), U.S. Pat 4889954 (1989-12-26) and European patent EP 0320694 (1988-11-29) have disclosed the method for preparing reduced content of nitrosamines long-chain alkyl amine oxide tensio-active agent.Chinese patent CN1328543 (2001-12-26), U.S. Pat 6121490 (2000-09-19), Japan special permission communique JP8157443 (1996-06-18), Japan special permission communique JP10182589 (1998-07-07) have disclosed a kind of method for preparing hydrogen peroxide low residue long-chain alkyl amine oxide tensio-active agent.
In recent years, the long-chain alkyl amine oxide tensio-active agent is used as the agent of industrial circulating water drag-reduction energy-saving and is come into one's own.Japan special permission communique JP2006199800 (2006-08-03), Japan special permission communique JP2004323813 (2004-11-18), Japan special permission communique JP2000198996 (2000-07-18), Japan special permission communique JP11029758 (1999-02-02) have disclosed and have a kind ofly used as the agent of recirculated water drag-reduction energy-saving with the long-chain alkyl amine oxide tensio-active agent, and the drag-reduction energy-saving agent prescription specificity that existing recirculated water drag-reduction energy-saving agent exists in using is strong to solve, Applicable temperature and the narrow problem of flow rates.Existing long-chain alkyl amine oxide tensio-active agent building-up process more complicated consumes a large amount of hydrogen peroxide raw materials, considers in the research that existing drag-reduction energy-saving agent interpolation concentration is higher, and the plain carbon stool pipeline is had obvious corrosive problem.
Summary of the invention
The purpose of this invention is to provide a kind of synthetic method, and use used as the agent of circulating water system drag-reduction energy-saving with chain alkyl dihydroxy ethyl amine oxide surfactant of drag reduction and corrosion inhibitive function.
Raw material chain alkyl diethanolamine industrial goods are produced by lauryl amine, palmitamide, hard ester amine, coco amine, beef tallow amine and soya-bean oil amine and oxyethane addition usually, and the adduct number of oxyethane is 1.6-2.4.Once " Speciality Petrochemicals " 2006, the 6th phase, disclosed coco amine polyoxyethylene (2) ether among 1-3 page or leaf and the Chinese patent ZL2006101298371 (2010-11-03) was the synthetic method of cocoyl diethanolamine to the contriver.
Discover that the chain alkyl diethanolamine is slightly soluble in water, not only as tensio-active agent, and also the industrial corrosion inhibitor that can be used as, corrosion inhibition rate can reach 94% when 50mg/L, and working concentration is 20-100mg/L usually.
Can be synthetic with hydrogen peroxide oxidation when chain alkyl dihydroxy ethyl amine oxide is used as the drag-reduction energy-saving agent by the chain alkyl diethanolamine, there is no need to add excess hydrogen peroxide in the building-up process raw material tertiary amine is transformed fully, unconverted raw material tertiary amine can be used as the plain metal pipeline corrosion inhibitor.
The synthetic technical scheme of taking of chain alkyl dihydroxy ethyl amine oxide is among the present invention:
Raw material chain alkyl diethanolamine is that carbon number is the single fat amine of C8-C22 and the affixture of oxyethane, also can be that coco amine, beef tallow amine and soya-bean oil amine are the mixing-in fat amine of representative and the affixture of oxyethane, the average adduct number of oxyethane be 1.6-2.4.The raw material hydrogen peroxide adopts industrial goods or the reagent of content more than 30%, needs accurately to analyze its content before using, and guarantees that feed ratio is accurate.Building-up process may further comprise the steps:
(1) raw material chain alkyl diethanolamine and deionized water are mixed the formation emulsion, be heated to 60-80 ℃;
(2) in reaction solution, slowly drip superoxol, the chain alkyl diethanolamine is oxidized to chain alkyl dihydroxy ethyl amine oxide, the mol ratio that adds hydrogen peroxide and chain alkyl diethanolamine is 0.9-0.95: 1, added the back insulation reaction 3-4 hour;
(3) regularly sampling detects tertiary amine content in the solution, when raw material tertiary amine transformation efficiency 90%-95%, adds a small amount of inferior sodium phosphate and decomposes residual hydrogen peroxide, detects residual hydrogen dioxide with starch/potassium iodide starch paper, adjusts amine oxide concentration to 40% in the solution.
The chain alkyl dihydroxy ethyl amine oxide technical scheme that application is taked as flow improver is among the present invention:
(1) with the inventive method synthetic chain alkyl dihydroxy ethyl amine oxide surfactant as flow improver, with unconverted raw material tertiary amine as inhibiter, strengthen the corrosion inhibitive function of chain alkyl dihydroxy ethyl amine oxide surfactant, flow improver and inhibiter mol ratio are 1 in the products obtained therefrom prescription: 0.05-0.1, form the circulating water system that is applicable to 5-60 ℃ of scope.
(2) with the drag-reduction energy-saving agent with effective concentration 0.2-1.0kg/m
3Amount add circulating water system and estimate, drag reducing efficiency reaches 50%-65%, corrosion inhibition rate reaches 98%-99%.
Among the present invention tertiary amine content measure be with hydrochloric acid in isopropanol solvent, be indicator with the thymol blue, drop reaction liquid and make sample behind the unhindered amina cationization with methyl iodide further calculates the tertiary amine transformation efficiency respectively.
Chain alkyl dihydroxy ethyl amine oxide surfactant carries out on indoor circuit flow improver evaluating apparatus as the validity of flow improver.
Evaluating apparatus is made up of pipeline and recirculated water storage tank, selected test section length 2m on the galvanized steel pipe of nominal diameter D15 and total length 4m, differential pressure pickup and flow sensor are installed, recirculated water is stored in the constant temperature and pressure jar of two 50L, adopts pressurized air as hydrodynamic force recirculated water to be carried between two basins.
For length and the certain pipeline of diameter, the coefficient of friction resistance is only relevant with the frictional resistance pressure drop under the same flow velocity.Therefore, drag reducing efficiency (DR) can be represented with the percentage of pipe ends frictional resistance pressure drop Δ P:
In the formula: Δ P
oPipe ends frictional resistance pressure drop for flow improver the time, Pa
Δ P
DRBe pipe ends frictional resistance pressure drop after the adding flow improver, Pa
By measuring the frictional resistance pressure drop of drag reducing fluid and non-drag reducing fluid under the same flow velocity, can calculate the drag reducing efficiency under this flow velocity, general Control Circulation water flow velocity 3m/s makes the recirculated water flow velocity enter turbulent area in the evaluation.
The rotary hanging plate method is adopted in the evaluation of flow improver corrosion inhibition rate: add certain density drag-reduction energy-saving agent in recirculated water, place 40 ± 1 ℃ constant temperature water bath, be fixed on lacing film device on plastic screw the test piece of having weighed and put into test solution, test period 72 hours.After the off-test, the test piece cleaning is weighed, calculate average corrosion rate.
Beneficial effect of the present invention is embodied in chain alkyl dihydroxy ethyl amine oxide synthetic method of the present invention and has simple and easy to do and the high advantage of raw material availability; Agent has broad application temperature range and the plain metal pipeline is had the characteristics of corrosion inhibitive function as the circulating water system drag-reduction energy-saving with it.
Embodiment
The present invention realizes in the following ways, describes in detail below in conjunction with embodiment:
Embodiment 1
In the 500mL four-hole reaction flask of mechanical stirrer, thermometer, dropping funnel, reflux condensing tube is housed, add lauryl amine polyoxyethylene (2) ether industrial goods 137g (0.5mol) and deionized water 80mL, mix the formation emulsion, be heated to 60 ℃, Dropwise 35 % hydrogen peroxide 48.9g (0.45mol) in 3 hours, control reaction temperature 60-80 ℃, added the back insulation reaction 4 hours.Period sampling measuring when tertiary amine transforms 90% when above, adds inferior sodium phosphate 1.5g and makes excessive hydrogen peroxide decomposition, with starch/potassium iodide starch paper detection residual hydrogen dioxide.With the solution cool to room temperature, obtain the colourless transparent solution of lauryl dihydroxy ethyl amine oxide content about 40%, standby.
Embodiment 2
In the 500mL four-hole reaction flask of mechanical stirrer, thermometer, dropping funnel, reflux condensing tube is housed, add coco amine polyoxyethylene (2) ether industrial goods 150g (0.5mol) and deionized water 100mL, mix the formation emulsion, be heated to 60 ℃, Dropwise 35 % hydrogen peroxide 48.9g (0.45mol) in 3 hours, control reaction temperature 60-80 ℃, added the back insulation reaction 4 hours.Period sampling measuring when tertiary amine transforms 90% when above, adds inferior sodium phosphate 1.5g and makes excessive hydrogen peroxide decomposition, with starch/potassium iodide starch paper detection residual hydrogen dioxide.With the solution cool to room temperature, obtain the colourless transparent solution of cocoyl dihydroxy ethyl amine oxide content about 40%, standby.
Embodiment 3
According to flow improver performance circuit evaluation method, on the flow improver device for evaluating performance,, add lauryl dihydroxy ethyl amine oxide (CDAO) the concentration 1000mg/L of embodiment 1 preparation to the differing temps tap water, under flow velocity 3m/s, carry out drag reducing efficiency and corrosion inhibition rate and measure measurement result such as table 1.Test result shows, lauryl dihydroxy ethyl amine oxide surfactant drag reducing efficiency and corrosion inhibition rate height.
Embodiment 4
According to flow improver performance circuit evaluation method, on the flow improver device for evaluating performance,, add cocoyl dihydroxy ethyl amine oxide (COAO) the concentration 1000mg/L of embodiment 2 preparations to the differing temps tap water, under flow velocity 3m/s, carry out drag reducing efficiency and corrosion inhibition rate and measure measurement result such as table 1.Test result shows, cocoyl dihydroxy ethyl amine oxide surfactant drag reducing efficiency and corrosion inhibition rate height, and the Applicable temperature scope is very wide.
Reference examples
According to flow improver performance circuit evaluation method, on the flow improver device for evaluating performance, to the differing temps tap water, add and to carry out drag reducing efficiency under flow improver cetyl trimethylammonium bromide (CTAB) the concentration 1000mg/L that adopts usually and assisting ion sodium salicylate (Sal) the concentration 500mg/L and corrosion inhibition rate is measured, measurement result is to such as table 1.
The different flow improvers of table 1 are when flow velocity 3m/s and drag reducing efficiency and corrosion inhibition rate in the differing temps recirculated water
| Flow improver is formed | DR(10℃) | DR(30℃) | DR(50℃) | Corrosion inhibition rate (40 ℃) | |
| Embodiment 3 | CDAO | 54.4％ | 62.3 | 57.6 | 98.7％ |
| Embodiment 4 | COAO | 60.2％ | 65.1 | 61.5 | 99.3％ |
| Reference examples | CTAB，Sal | 41.2 | 53.1 | 45.6 | 64.3％ |
Claims (6)
1. method with hydrogen peroxide oxidation chain alkyl diethanolamine synthesizing long-chain alkyl dihydroxy ethyl amine oxide, it is characterized in that controlling raw material tertiary amine transformation efficiency 90%-95%, unconverted raw material amine is as inhibiter, strengthen the corrosion inhibitive function of chain alkyl dihydroxy ethyl amine oxide surfactant, said method comprising the steps of:
(1) raw material chain alkyl diethanolamine and deionized water mix the formation emulsion, are heated to 60-80 ℃;
(2) drip superoxol oxidation chain alkyl diethanolamine, added the back insulation reaction 3-4 hour;
(3) when raw material amine transformation efficiency 90%-95%, add inferior sodium phosphate and decompose residual hydrogen peroxide, adjust amine oxide concentration to 40% in the solution.
2. according to the described method of claim 1, it is characterized in that the chain alkyl diethanolamine is that carbon number is the aliphatic amide of C8-C22 and the affixture of oxyethane, the average adduct number of oxyethane is 1.6-2.4.
3. according to the described method of claim 1, it is characterized in that the chain alkyl diethanolamine is the affixture of coco amine, beef tallow amine and soya-bean oil amine and oxyethane, the average adduct number of oxyethane is 1.6-2.4.
4. according to the described method of claim 1, the mol ratio that it is characterized in that adding in the building-up process hydrogen peroxide and chain alkyl diethanolamine is 0.9-0.95: 1.
5. the method used as flow improver of an amine oxide surfactant, it is characterized in that with the described method synthetic of claim 1 chain alkyl dihydroxy ethyl amine oxide surfactant as flow improver, with unconverted raw material tertiary amine as inhibiter, flow improver and inhibiter mol ratio are 1: 0.05-0.1, form the circulating water system flow improver that is applicable to 5-60 ℃ of temperature range.
6. according to the described flow improver application method of claim 5, it is characterized in that the drag-reduction energy-saving agent is with effective concentration 0.2-1.0kg/m
3Amount add circulating water system and estimate, drag reducing efficiency reaches 50%-65%, corrosion inhibition rate reaches 98%-99%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100226555A CN102153491A (en) | 2011-01-20 | 2011-01-20 | Synthesis method of long-chain alkyl dihydroxyethyl amine oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100226555A CN102153491A (en) | 2011-01-20 | 2011-01-20 | Synthesis method of long-chain alkyl dihydroxyethyl amine oxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102153491A true CN102153491A (en) | 2011-08-17 |
Family
ID=44435213
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011100226555A Pending CN102153491A (en) | 2011-01-20 | 2011-01-20 | Synthesis method of long-chain alkyl dihydroxyethyl amine oxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102153491A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104507909A (en) * | 2012-07-24 | 2015-04-08 | 宝洁公司 | Continuous process to make amine oxide |
| CN106062059B (en) * | 2013-12-18 | 2019-07-05 | 液化动力专业产品公司 | Aqueous fluidity improver preparaton for refined products |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4889954A (en) * | 1988-06-30 | 1989-12-26 | Ethyl Corporation | Amine oxide process |
| US5583258A (en) * | 1995-02-15 | 1996-12-10 | The Procter & Gamble Company | Process for preparing mono-long chain amine oxide surfactants |
| JP2006199800A (en) * | 2005-01-19 | 2006-08-03 | Toho Chem Ind Co Ltd | Composition for reducing water transportation drag |
| CN1887861A (en) * | 2005-06-29 | 2007-01-03 | 上海高维化学有限公司 | Prepn of alkyl amidopropyldimethyl amine oxide surfactant |
-
2011
- 2011-01-20 CN CN2011100226555A patent/CN102153491A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4889954A (en) * | 1988-06-30 | 1989-12-26 | Ethyl Corporation | Amine oxide process |
| US5583258A (en) * | 1995-02-15 | 1996-12-10 | The Procter & Gamble Company | Process for preparing mono-long chain amine oxide surfactants |
| JP2006199800A (en) * | 2005-01-19 | 2006-08-03 | Toho Chem Ind Co Ltd | Composition for reducing water transportation drag |
| CN1887861A (en) * | 2005-06-29 | 2007-01-03 | 上海高维化学有限公司 | Prepn of alkyl amidopropyldimethyl amine oxide surfactant |
Non-Patent Citations (1)
| Title |
|---|
| 王成等: "有机胺对铝合金在3.5%氯化钠溶液中的缓蚀作用", 《腐蚀与防护》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104507909A (en) * | 2012-07-24 | 2015-04-08 | 宝洁公司 | Continuous process to make amine oxide |
| CN104507909B (en) * | 2012-07-24 | 2017-05-31 | 宝洁公司 | Prepare the continuation method of amine oxide |
| CN106062059B (en) * | 2013-12-18 | 2019-07-05 | 液化动力专业产品公司 | Aqueous fluidity improver preparaton for refined products |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1676831B1 (en) | N,N-dialkylpolyhydroxyalkylamines | |
| CN106397276B (en) | The production method of AEO sulfonated bodies | |
| CN105568300B (en) | A kind of pyridine quaternary ammonium salt corrosion inhibiter and preparation method thereof for industry cleaning link | |
| JPH11501694A (en) | Use of betaine surfactants in combination with anionic surfactants as drag reducing agents | |
| CN109208016A (en) | A kind of without phosphorus anti-rust metal detergent and preparation method thereof | |
| CN102153491A (en) | Synthesis method of long-chain alkyl dihydroxyethyl amine oxide | |
| Yunling et al. | Synthesis, characterization and surface‐activity of hydroxyethyl group‐containing quaternary ammonium surfactants | |
| Xu et al. | Fouling characterization of calcium carbonate on heat transfer surfaces with sodium carboxymethyl cellulose as an inhibitor | |
| CN102093240A (en) | Synthesis method of fatty acid monoethanal acid amide | |
| CN110354755A (en) | A kind of novel fluorine betaine type amphoteric surfactant and its preparation method and application | |
| CN106496059A (en) | The process of free acid in a kind of reduction glycine betaine | |
| Rahimov et al. | Coconut oil fatty acid ammonium-type salts | |
| CN100554517C (en) | A kind of preparation method of high-concentration gasified rust-proofing liquor | |
| CN108179426A (en) | A kind of copper and its alloy pickling corrosion inhibiter and preparation method thereof | |
| CN100526281C (en) | Method of synthesizing 3-methoxy-4-dydroxymandelic acid or 3-ethoxy-4-dydroxymandelic acid by acetaldehyde acid method | |
| CN103804562A (en) | Non-phosphorus copolymer antiscale dispersant and preparation method thereof | |
| CN112591905B (en) | Efficient slime stripping agent and preparation method thereof | |
| US20200284277A1 (en) | Drag Reducing Agents and Methods of Using Thereof | |
| JP2000313872A (en) | Method for decreasing in-pipe friction resistance of water-based heat transfer medium | |
| US20060020144A1 (en) | Bis(3-alkoxyalkan-2-OL) sulfides, sulfones, and sulfoxides: new surface active agents | |
| CN102766064B (en) | Preparation method of fluorocarbon foaming agent N-(2-hydroxy propyl) perfluorocaprylamide | |
| CN105565515B (en) | A kind of composite scale-inhibiting corrosion inhibitor and its application in circulating water cooling treatment | |
| SE502764C2 (en) | Use of an alkoxylated alkanolamine together with an alkoxylated alcohol as a friction reducing agent | |
| CN105315983B (en) | Aqueous fracturing fluid drag reducer and its preparation method and application | |
| CN105273708A (en) | Drag reducer for fracturing fluid, and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20110817 |