CN103450471B - A kind of composite natural gas flow improver and preparation method thereof - Google Patents
A kind of composite natural gas flow improver and preparation method thereof Download PDFInfo
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- CN103450471B CN103450471B CN201310397752.1A CN201310397752A CN103450471B CN 103450471 B CN103450471 B CN 103450471B CN 201310397752 A CN201310397752 A CN 201310397752A CN 103450471 B CN103450471 B CN 103450471B
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Abstract
The invention discloses a kind of composite natural gas flow improver and preparation method thereof.The method comprises the steps: that the monocarboxylic acid of organic dibasic acid or organic dibasic acid acid anhydride, organic amine and Long carbon chain carries out reacting and obtain described composite natural gas flow improver; The concrete steps of described reaction are as follows: (1) under an inert atmosphere, described organic dibasic acid or described organic dibasic acid acid anhydride and described organic amine react; (2) under an inert atmosphere, the monocarboxylic acid of described Long carbon chain is added in the reaction system after terminating to reaction described in step (1), through reacting and obtaining described composite natural gas flow improver.Composite natural gas flow improver of the present invention is obvious to pipeline gas drag reduction, energy-saving effect, and cheaper starting materials is easy to get, simple to operate, reaction conditions is gentle, process is simple, low for equipment requirements, is easy to realize suitability for industrialized production.
Description
Technical field
The present invention relates to a kind of composite natural gas flow improver and preparation method thereof.
Background technology
Come from the pressure of consideration to environment and world's carbon discharge capacity, various countries are honest to be tried hard to recommend dynamic Sweet natural gas and produces and efficiency utilization, replaces coal and oil with part.Sweet natural gas is as a kind of clean energy, and its status in world energy sources general layout improves constantly.And along with the continuous growth of natural gas energy resource demand and the needs of peak regulation, make world's natural gas transport technology face larger challenge.Improve transport capacity and the regulating power of natural gas line, except building more massive natural gas line and pipe network, the transporting resistance also by reducing existing pipeline realizes.Sweet natural gas flow improver drag reduction technology increases defeated new technology as a kind of drag reduction, receives the extensive concern of domestic and international research institution.Meanwhile, natural gas line also also exists serious corrosion and ageing problem, especially gathering line and gas field pipe network.The working life of natural gas line is reduced, potential safety hazard increase.Therefore, the Sweet natural gas flow improver with drag reduction and inhibition multi-efficiency is developed extremely urgent.Namely reach drag reduction and increase defeated object, slow down again corrosive pipeline, extend pipeline working life, improve conduit running safety.
Whether Sweet natural gas flow improver not only can be used for new pipeline, also can be used for the transformation of old pipeline, and have undercoat not affect the application of Sweet natural gas flow improver in old pipeline.Sweet natural gas flow improver is as a kind of novel pipeline chemical additive and products that save energy and resources, and its effect to be bonded in tube metal internal surface fill pipe internal surface " trench " securely, and form the smooth elasticity liquid film of one deck.One is the effect playing " filling out hole ", reduces the degree of roughness of wall.The reduction of roughness effectively reduces the coefficient of friction resistance, thus reduces kinetic equation loss, increases operational throughput.Two is form flexible wall.Flexible wall reduces turbulent flow odds on the one hand; Ejection in bursting process can be partially absorbed on the other hand, scan quasi-periodic like this kinergety, reduce turbulence intensity.Meanwhile, because Sweet natural gas flow improver partly or completely covers inner surface of pipeline, the same with inhibiter have effect that change metallic surface character reduces its etching extent.Therefore, reasonably carry out molecular designing and must synthesize the Sweet natural gas flow improver with the defeated and anticorrosion multi-efficiency of drag reduction increasing: can avoid repeatedly injecting dissimilar pipeline additives, reduce operation and cost of investment; Interaction between can avoiding because of different additive and the potential safety hazard caused.
Summary of the invention
The object of this invention is to provide a kind of composite natural gas flow improver and preparation method thereof, preparation method of the present invention is simple, and the drag-reduction effect of the composite natural gas flow improver of preparation is good, validity period long, have preservative activity.
The preparation method of a kind of composite natural gas flow improver provided by the present invention, comprises the steps:
The monocarboxylic acid of organic dibasic acid or organic dibasic acid acid anhydride, organic amine and Long carbon chain carries out reacting and obtain described composite natural gas flow improver;
Described organic dibasic acid can be oxalic acid, oxaloacetic acid, propanedioic acid, succinic acid, hydroxy-butanedioic acid, pentanedioic acid, α-ketoglutaric acid, tartrate, methylene-succinic acid, iminodiethanoic acid, hexanodioic acid, phthalic acid, m-phthalic acid or terephthalic acid;
Described organic dibasic acid acid anhydride can be Succinic anhydried, MALEIC ANHYDRIDE or Tetra hydro Phthalic anhydride;
Described organic amine can be quadrol, hydroxyethylethylene diamine, triethylene diamine, hexanediamine, O-Phenylene Diamine, mphenylenediamine, Ursol D, diethylenetriamine, triethylene tetramine, tetraethylene pentamine or polyethylene polyamine; The molecular weight of described polyethylene polyamine is 60 ~ 240gmol
-1;
The monocarboxylic acid of described Long carbon chain can be phenylformic acid, n-caprylic acid, n-capric acid, lauric acid, Palmiticacid, stearic acid, oleic acid, sylvic acid, nondecylic acid, docosoic acid, Lignoceric acid, hexacosanoic acid or triacontanoic acid.
In above-mentioned preparation method, the concrete steps of described reaction are as follows:
(1) under an inert atmosphere, described organic dibasic acid or described organic dibasic acid acid anhydride and described organic amine react;
(2) under an inert atmosphere, the monocarboxylic acid of described Long carbon chain is added in the reaction system after terminating to reaction described in step (1), through reacting and obtaining described composite natural gas flow improver.
In above-mentioned preparation method, in step (1), the mol ratio of described organic dibasic acid or described organic dibasic acid acid anhydride and described organic amine can be 1:1.5 ~ 2.5, as 1:2;
Described in step (1), the temperature of reaction can be 150 ~ 230 DEG C, and the time can be 2 ~ 12h, as reacted 4 hours under the condition of 190 DEG C.
In above-mentioned preparation method, in step (2), the mol ratio of the monocarboxylic addition of described Long carbon chain and described organic dibasic acid or described organic dibasic acid acid anhydride can be 1 ~ 2.0:1, as 2.0:1;
Described in step (1), the temperature of reaction can be 130 ~ 210 DEG C, and the time can be 2 ~ 12h, as reacted 4 hours under the condition of 190 DEG C.
The present invention still further provides the composite natural gas flow improver prepared by aforesaid method.
The principle of foundation of the present invention: utilize the special macromolecular cpd with the similar constructional feature of tensio-active agent or oligopolymer, its polar end is firmly adsorbed on metallic conduit internal surface, non-polar end stretches to bodies of fluid, thus form the fine and close liquid film that one deck has suitable thickness, play " filling out hole " effect.Reduce inner wall coarse degree.Due to the special construction that liquid film has, partly can absorb ejection in bursting process, scan so quasi-periodic kinergety, reduce turbulence intensity; On the other hand because the flexibility of liquid film can reduce wall turbulent flow odds, reach drag reduction object.Change the interfacial property of metal simultaneously, prevent the chance of corrosive medium and tube contacts, reach anticorrosion object.
Composite natural gas flow improver of the present invention is obvious to pipeline gas drag reduction, energy-saving effect, and cheaper starting materials is easy to get, simple to operate, reaction conditions is gentle, process is simple, low for equipment requirements, is easy to realize suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is the corrosion inhibition rate design sketch of composite natural gas flow improver in the hydrochloric acid soln of 10% prepared by the embodiment of the present invention 1.
Fig. 2 is the corrosion inhibition rate effect picture of flow improver Q235 carbon steel coupon in the hydrochloric acid soln of 10% adding the preparation of different concns embodiment 1.
Fig. 3 is electron microscope photo scanning, and wherein, left figure is the electron microscope photo scanning on blank Q235 carbon steel coupon surface, and right figure is the electron microscope photo scanning after Q235 carbon steel coupon soaks in the ethanolic soln (10wt%) of this flow improver.
Fig. 4 is the drag reducing efficiency variation diagram of the static state filling evaluation experimental of flow improver prepared by the embodiment of the present invention 1.
Fig. 5 is the drag reducing efficiency variation diagram of the indoor circuit experiment of flow improver prepared by the embodiment of the present invention 1.
Embodiment
The experimental technique used in following embodiment if no special instructions, is ordinary method.
Material used in following embodiment, reagent etc., if no special instructions, all can obtain from commercial channels.
Embodiment 1, prepare composite natural gas flow improver
By 16.6g(0.1mol) phthalic acid and 20.6g(0.2mol) diethylenetriamine join in the there-necked flask of 250ml; under the protection of rare gas element; mixing control temperature of reaction is 190 DEG C; reaction 4h; in time substantially not having water to produce (now water outlet is about 3.6g); stopped reaction, cooling when temperature drops to below 100 DEG C, the 58.4g(0.2mol by having weighed up) oleic acid join in 250ml reactor.Under the protection of rare gas element, stir intensification and control to be 190 DEG C, to continue reaction 4h in temperature.In time substantially not having water to produce (now water outlet is about 3.6g), stopped reaction, when cooling temperature is lower than less than 100 DEG C, the thick product poured out.Thick product is dissolved in the middle of alcohol, namely can be used as composite natural feed channel flow improver.
The composite natural feed channel flow improver obtained by the present embodiment, takes a morsel and is dissolved in the middle of alcohol.Then its corrosion inhibition rate to Q235 carbon steel is surveyed with method of static coupon.Experiment condition is: 15 DEG C, and concentration of hydrochloric acid is 10%, and the lacing film time is 72h, and record the corrosion inhibition rate change curve of different concns flow improver in hydrochloric acid, as shown in Figure 1, can be learnt by Fig. 1, its corrosion inhibition rate reaches 99% when 50mg/L.
Figure 2 shows that and add the corrosion inhibition rate effect picture of different concns flow improver Q235 carbon steel coupon in the hydrochloric acid soln of 10%, wherein, Zuo Tuzhong, the concentration of flow improver is followed successively by 0(as blank from left to right), 0.5 × 10
-5mg/L, 1.0 × 10
-5mg/L, 1.5 × 10
-5mg/L, 2.0 × 10
-5mg/L and 2.5 × 10
-5the corrosion sample of mg/L, in right figure, the concentration of flow improver is followed successively by 0(as blank from left to right), 0.5 × 10
-4mg/L, 1.0 × 10
-4mg/L, 1.5 × 10
-4mg/L, 2.0 × 10
-4mg/L, 2.5 × 10
-4mg/L and 3.0 × 10
-4the corrosion sample of mg/L, as can be seen from this figure, along with the increase of this flow improver concentration, the degree of roughness on steel disc surface obviously reduces, namely the extent of corrosion of hydrochloric acid to it obviously reduces, illustrate that this flow improver forms good adsorption film on steel disc surface, can effectively prevent hydrochloric acid to the corrosion of steel disc.
In Fig. 3, left figure is the electron microscope photo scanning on blank Q235 carbon steel coupon surface, right figure is the electron microscope photo scanning after Q235 carbon steel coupon soaks in the ethanolic soln (10wt%) of this flow improver, the film-formation result contrasted with steel disc blank under multiplying power and flow improver can find, this flow improver has good absorption film-forming performance on carbon steel coupon surface, clearly be filled with the roughness on steel disc surface, and then the effect reducing fluid flow resistance can be played, show the potential using value as gas pipeline drag reduction agent.
The flow improver prepared by the present embodiment is applied to indoor circuit evaluation:
1, static pre-film 2h, flow is 124Nm
3h
-1time, after stable, average drag reducing efficiency can reach 11%, maximum drag reducing efficiency 12%, and drag reducing efficiency change is as indicated at 4.
As seen from Figure 4, along with the increase of filling rate, drag-reduction effect first significantly raises, after slowly tend towards stability, be finally stabilized in 11%.
2, adopt the mode of atomization filling to carry out evaluation test, filling speed is 4L/h, annotates 3 hours, test traffic 125Nm
3h
-1time, after stable, average drag reducing efficiency reaches 18%, and maximum drag reducing efficiency can reach 19%, and drag reducing efficiency change is as figure 5 illustrates.
As seen from Figure 5, along with the increase of filling rate, drag-reduction effect significantly raises, and finally slowly tends towards stability, and reaches certain value 18%.Comparison diagram 4 and Fig. 5 can find, adopt the mode successful of atomization filling to be better than static pre-film, illustrate that atomization filling can make flow improver form more stable film at pipe surface.
Claims (4)
1. a preparation method for composite natural gas flow improver, comprises the steps:
(1) under an inert atmosphere, organic dibasic acid or organic dibasic acid acid anhydride and organic amine react;
(2) under an inert atmosphere, the monocarboxylic acid of Long carbon chain is added in the reaction system after terminating to reaction described in step (1), through reacting and obtaining described composite natural gas flow improver;
Described organic dibasic acid is oxalic acid, oxaloacetic acid, propanedioic acid, succinic acid, hydroxy-butanedioic acid, pentanedioic acid, α-ketoglutaric acid, tartrate, methylene-succinic acid, iminodiethanoic acid, hexanodioic acid, phthalic acid, m-phthalic acid or terephthalic acid;
Described organic dibasic acid acid anhydride is Succinic anhydried, MALEIC ANHYDRIDE or Tetra hydro Phthalic anhydride;
Described organic amine is diethylenetriamine, triethylene tetramine, tetraethylene pentamine or polyethylene polyamine; The molecular weight of described polyethylene polyamine is 60 ~ 240gmol
-1;
The monocarboxylic acid of described Long carbon chain is phenylformic acid, n-caprylic acid, n-capric acid, lauric acid, Palmiticacid, stearic acid, oleic acid, sylvic acid, nondecylic acid, docosoic acid, Lignoceric acid, hexacosanoic acid or triacontanoic acid.
2. preparation method according to claim 1, is characterized in that: in step (1), and the mol ratio of described organic dibasic acid or described organic dibasic acid acid anhydride and described organic amine is 1:1.5 ~ 2.5;
Described in step (1), the temperature of reaction is 150 ~ 230 DEG C, and the time is 2 ~ 12h.
3. preparation method according to claim 2, is characterized in that: in step (2), and the mol ratio of the monocarboxylic addition of described Long carbon chain and described organic dibasic acid or described organic dibasic acid acid anhydride is 1 ~ 2.0:1;
Described in step (2), the temperature of reaction is 130 ~ 210 DEG C, and the time is 2 ~ 12h.
4. the composite natural gas flow improver prepared of method according to any one of claim 1-3.
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| CN103980869B (en) * | 2014-04-22 | 2018-04-24 | 中石化石油工程技术服务有限公司 | A kind of oil base drilling fluid solid emulsifier and preparation method and the application in oil base drilling fluid |
| CN105601798B (en) * | 2016-01-04 | 2017-07-18 | 钦州学院 | The shale gas exploitation preparation method of abietyl drag reducer |
| US11492544B2 (en) * | 2016-06-22 | 2022-11-08 | Hexion Inc. | Chemical products for adhesive applications |
| CN109477366B (en) * | 2016-06-22 | 2022-07-01 | 瀚森公司 | Chemical products for adhesive applications |
| CN110467912B (en) * | 2019-09-10 | 2021-06-25 | 肯特催化材料股份有限公司 | High-temperature triggered wetting reversal agent and preparation method and application thereof |
| CN113214473B (en) * | 2021-05-12 | 2022-05-17 | 长江大学 | Preparation method and application of low-permeability reservoir water injection well pressure-reducing and injection-increasing polyamide |
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| CN101463130A (en) * | 2008-07-10 | 2009-06-24 | 金发科技股份有限公司 | Semi-aromatic polyamide and low wastewater discharge preparation thereof |
| CN101570687A (en) * | 2008-04-30 | 2009-11-04 | 中国石油天然气股份有限公司 | Oilfield injection friction-reducing agent and application thereof |
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| CN101570687A (en) * | 2008-04-30 | 2009-11-04 | 中国石油天然气股份有限公司 | Oilfield injection friction-reducing agent and application thereof |
| CN101463130A (en) * | 2008-07-10 | 2009-06-24 | 金发科技股份有限公司 | Semi-aromatic polyamide and low wastewater discharge preparation thereof |
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Address after: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Co-patentee after: CNOOC research institute limited liability company Patentee after: China Offshore Oil Group Co., Ltd. Co-patentee after: China Petroleum University (East China) Address before: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Co-patentee before: CNOOC Research Institute Patentee before: China National Offshore Oil Corporation Co-patentee before: China Petroleum University (East China) |