CN102993431B - Preparation and application methods of polyepoxysuccinic acid derivative scale inhibitor - Google Patents
Preparation and application methods of polyepoxysuccinic acid derivative scale inhibitor Download PDFInfo
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- CN102993431B CN102993431B CN201210521434.7A CN201210521434A CN102993431B CN 102993431 B CN102993431 B CN 102993431B CN 201210521434 A CN201210521434 A CN 201210521434A CN 102993431 B CN102993431 B CN 102993431B
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Abstract
The invention provides a polyepoxysuccinic acid derivative scale inhibitor. A preparation method of the polyepoxysuccinic acid derivative scale inhibitor comprises the step of cyclization reaction and purifying of a cyclized product, preparation of a polyepoxysuccinic acid product, and the step of preparation of polyepoxysuccinic acid derivative Lcys-PESA (Polyepoxysuccinic Acid). The preparation method comprises the following concrete steps in sequence: placing the product of PESA into a three-necked flask; adding L-cysteine; transferring the three-necked flask in a methylsilicone oil bath to heat until reaching 110 to 120 DEG C; starting to adjust the pH; fully stirring to react; drying through a drying device, so as to obtain an L-cysteine modified polyepoxysuccinic acid derivative; porphyrizing; and storing in a seal way to stand by service. The polyepoxysuccinic acid derivative scale inhibitor is applied to the conditions with temperature of 55 to 85 DEGC, pH of 5.0 to 10.0, and scale inhibiting ratio of 90 to 98%. According to the preparation and application methods of the polyepoxysuccinic acid derivative scale inhibitor, small molecular substances, which are free from phosphorus and nontoxic, brings no damage to the ecological environment and are higher in biodegradability and water solubility, are added during synthesizing; and the polyepoxysuccinic acid derivative scale inhibitor excellent in scale inhibiting and dispersing performance is specially suitable for being applied to treatment of industrial water.
Description
Technical field
The present invention relates to a kind of preparation and Application Areas of poly-epoxy succinic acid derivative Scale inhibitors.Relate in particular to a kind of preparation and application method thereof for water conditioner poly-epoxy succinic acid derivative Scale inhibitors with environmentally friendly biological degradability and water soluble characteristic.
Background technology
Along with low-carbon (LC), environmental protection, sustainable development idea gradually deeply, also there is great change in the developing direction of global chemical research, its mark is exactly the proposition of " Green Chemistry (chemical industry) " concept.And it is subject to people's attention day by day.Green Chemistry, uses chemical technology and method exactly, fundamentally reduces or eliminates those generation and application to human health or harmful raw material, product, by product, solvent and the reagent etc. of environment.Along with social development, more and more advocate Green Chemistry.In industrial water system, the formation of dirt is the second largest main harm except material and facility corrosion.Scale inhibitors mainly refers to and can prevent that incrustation scale and dirt from producing or suppressing the chemical classes reagent of its deposition growing, is requisite element in Treatment of Industrial Water, can be used for extension device life-span ensure equipment safety operation.At present, the research of Scale inhibitors is also constantly being goed deep into and is being reached its maturity, and its feature and function are also being gradually improved.Meanwhile, the kind of Scale inhibitors is also in continuous increase.
Along with early 1990s U.S. Betz laboratory is since development in laboratory goes out the without phosphorus poly-epoxy succinic acid without nitrogen (PESA) Green Water Treatment Reagents, investigator studies its performance in succession both at home and abroad.But single PESA scale-inhibiting properties in the time of lower concentration is general, and add concentration and can cause when high the raising of production cost.Research shows to optimize synthesis condition by synthetic PESA derivative, PESA is had multi-functional, is the new trend to the research of PESA Scale inhibitors.
Summary of the invention
The present invention is high in order to solve existing Scale inhibitors use cost, low and the environmentally harmful problem of scale inhibition efficiency, one is to provide one adds a kind of small-molecule substance in synthetic, increase the scale-inhibiting properties of poly-epoxy succinic acid, in water, solvability is good, nontoxic to environment, biodegradable, have multi-functional, the poly-epoxy succinic acid derivative Scale inhibitors synthetic method that scale inhibition efficiency is high, two are to provide a kind of application method of poly-epoxy succinic acid derivative Scale inhibitors.
Realize above-mentioned purpose by the following technical solutions: a kind of poly-epoxy succinic acid derivative Scale inhibitors, described method comprises the steps: cyclization and the purification of cyclisation product: it is epoxy sodium succinate that this step obtains white solid; The preparation of poly-epoxy succinic acid product: epoxy sodium succinate is packed in there-necked flask, put into methyl-silicone oil and bathe heating, be raised to after 80 DEG C-88 DEG C until temperature, starting to add calcium hydroxide initiator, add altogether calcium hydroxide initiator three to four times, is then that 40%NaOH regulates pH>12 by mass percent, fully after stirring reaction, product is put into acidifying alcohol solution and wash, leave standstill separatory, obtain poly-epoxy succinic acid PESA; Also comprise the preparation of poly-epoxy succinic acid derivative Lcys-PESA, its preparation method is: the product of poly-epoxy succinic acid PESA is put into there-necked flask, divide the Cys that adds 1.5g-3.0g for 2-3 time, put into methyl-silicone oil and bathe heating, be raised to after 110 DEG C-120 DEG C until temperature, start to regulate pH between 4.0-6.0, fully after stirring reaction 2.5h-3.5h, when reaction system becomes orange-yellow thick thing, stop heating, after dry with drying installation, obtain Cys modified poly-epoxy succinic acid derivative Lcys-PESA, porphyrize is airtight to be saved backup.
As preferred version, the molecular structural formula of described Cys is:
As preferred version, by weight, poly-epoxy succinic acid PESA and Cys ratio are 10:1.
As preferred version, described drying installation is ultra red ray drying lamp.
As preferred version, described Cys modified poly-epoxy succinic acid derivative Lcys-PESA finished product is ground to 60 orders with shredder
An application method for poly-epoxy succinic acid derivative Scale inhibitors, described poly-epoxy succinic acid derivative Scale inhibitors is 55 DEG C-85 DEG C in temperature, and pH value is 5.0～10.0, and scale inhibition performance is applied in the scope of 90%-98%.
Adopt technique scheme; owing to containing a large amount of carboxylic groups in poly-epoxy succinic acid; and carboxyl can with a lot of group generation acylation reactions; especially with to contain amino organic compound reaction better; generate amides; and amino acid has more functional group, amino acid and PESA can be reacted, generate acyl group Cys compounds.Increase so the larger easy complexing atom number of electronegativity, thereby further improve original poly-epoxy succinic acid complex ability, finally play the object that improves scale inhibitor efficiency.
Poly-epoxy succinic acid derivative Scale inhibitors prepared by the present invention, belongs to polymer-type Scale inhibitors.Not phosphorous, nontoxic in poly-epoxy succinic acid derivative (Lcys-PESA) molecule, do not destroy ecotope and there is good biodegradability and water-soluble, its excellent scale inhibition and dispersion performance is specially adapted to Treatment of Industrial Water.Its significant effect is also: the processing condition that need not change other, just in synthetic, add a kind of small-molecule substance, improve its linear structure, PESA has multi-functional, and reached the object that increases the scale inhibition dispersion effect of poly-epoxy succinic acid, further widen the range of application of poly-epoxy succinic acid.
Brief description of the drawings
Fig. 1 is that temperature of the present invention affects schematic diagram to Lcys-PESA scale-inhibiting properties.
Fig. 2 is the schematic diagram of pH of the present invention on the impact of Lcys-PESA scale-inhibiting properties.
Fig. 3, Fig. 4, Fig. 5 is respectively calcium carbonate crystalline form SEM figure of the present invention.
Embodiment
Below in conjunction with embodiment, the invention will be further described.
The present embodiment is a kind of preparation and application side of poly-epoxy succinic acid derivative Scale inhibitors
Method, its invention thought is, in the poly-epoxy succinic acid derivative preparation process of (being called for short Lcys-PESA), repeatedly adds L-half Guang ammonia, improves scale inhibitor efficiency, the molecular structural formula of Cys is:
Poly-epoxy succinic acid derivative Scale inhibitors preparation method embodiment:
Embodiment 1:
A. cyclization and cyclisation product are purified
A adds 16gNaOH in there-necked flask, and adds 36ml water, and there-necked flask is put into magnetic agitation water-bath, after fully dissolving, adds 19.6g maleic anhydride, simultaneously warming-in-water to 55 DEG C under magnetic agitation.After warming-in-water to 55 DEG C, add catalyzer 1.2gNa
2wO
4.Be warming up to 70 DEG C to water-bath afterwards, after temperature-stable, in 35min, evenly drip hydrogen peroxide 24ml with separating funnel.Now start to regulate in pH=6-7 with 1:1 hydrochloric acid soln, react and obtain mixing thick product after 1.5 hours.
B product is purified: thick the mixing of step a product is heated with electric mantle, vacuumize simultaneously and carry out underpressure distillation.Residual solution to be evaporated is 1/2 o'clock of original solution volume, stops underpressure distillation.Pour in ready dehydrated alcohol solution into precipitating 2 times.Obtain white needle-like crystals, put into air dry oven continuous drying 75h under the environment of 60 DEG C, obtain white solid, be purer epoxy sodium succinate.
B. the preparation of poly-epoxy succinic acid product
Getting the epoxy sodium succinate that step b makes packs in there-necked flask, put into methyl-silicone oil and bathe heating, be raised to after 85 DEG C until temperature, start to add 1.2g calcium hydroxide initiator, divide and add for 3 times, add once every 5min, rear is that 40%NaOH regulates pH>12 by mass percent.Fully, after stirring reaction 2h, in the time that solution becomes the thick thing of light khaki color, stop heating.Secondly, product is put into acidifying alcohol solution and wash 3 times, leave standstill separatory, collect lower floor's thickness wax.Both obtained poly-epoxy succinic acid (PESA).
C. the preparation of poly-epoxy succinic acid derivative (being called for short Lcys-PESA)
The product of step B is put into there-necked flask, divide the Cys that adds 1.5g for 2 times, put into methyl-silicone oil and bathe heating, be raised to after 110 DEG C until temperature, start to regulate pH 4, fully after stirring reaction 3.5h, stop heating, obtain Melon yellow look thick thing, dry under infrared drying lamp.Both poly-epoxy succinic acid derivative Lcys-PESA, airtight the saving backup of porphyrize 60 orders had been obtained.
Embodiment 2:
A. cyclization and cyclisation product are purified
A adds 13gNaOH in there-necked flask, and adds 35ml water, and there-necked flask is put into magnetic agitation water-bath, after fully dissolving, adds 18g maleic anhydride, simultaneously warming-in-water to 52 DEG C under magnetic agitation.After warming-in-water to 52 DEG C, add catalyzer 1gNa
2wO
4.Be warming up to 65 DEG C to water-bath afterwards, after temperature-stable, in 30min, evenly drip hydrogen peroxide 20ml with separating funnel.Now start to regulate in pH=6-7 with 1:1 hydrochloric acid soln, react and obtain mixing thick product after 1 hour.
B product is purified: thick the mixing of step a product is heated with electric mantle, vacuumize simultaneously and carry out underpressure distillation.Residual solution to be evaporated is 1/2 o'clock of original solution volume, stops underpressure distillation.Pour in ready dehydrated alcohol solution into precipitating 2 times.Obtain white needle-like crystals, put into air dry oven continuous drying 72h under the environment of 60 DEG C, obtain white solid, be purer epoxy sodium succinate.
B. the preparation of poly-epoxy succinic acid product
Getting the epoxy sodium succinate that step b makes packs in there-necked flask, put into methyl-silicone oil and bathe heating, be raised to after 80 DEG C until temperature, start to add 1g calcium hydroxide initiator, divide and add for three times, add once every 5min, rear is that 40%NaOH regulates pH>12 by mass percent.Fully, after stirring reaction 2h, in the time that solution becomes the thick thing of light khaki color, stop heating.Secondly, product is put into acidifying alcohol solution and wash 3 times, leave standstill separatory, collect lower floor's thickness wax.Both obtained poly-epoxy succinic acid (PESA).
C. the preparation of poly-epoxy succinic acid derivative (being called for short Lcys-PESA)
The product of step B is put into there-necked flask, divide the Cys that adds 2.0g for 2 times, put into methyl-silicone oil and bathe heating, be raised to after 115 DEG C until temperature, start to regulate pH 6, fully after stirring reaction 2.5h, stop heating, obtain Melon yellow look thick thing, dry under infrared drying lamp.Both poly-epoxy succinic acid derivative Lcys-PESA, airtight the saving backup of porphyrize 60 orders had been obtained.
Embodiment 3:
A. cyclization and cyclisation product are purified
A adds 18gNaOH in there-necked flask, and adds 38ml, and there-necked flask is put into magnetic agitation water-bath, after fully dissolving, adds 20g maleic anhydride, simultaneously warming-in-water to 58 DEG C under magnetic agitation.After warming-in-water to 58 DEG C, add catalyzer 1.5gNa
2wO
4be warming up to 75 DEG C to water-bath afterwards, after temperature-stable, in 40min, evenly drip hydrogen peroxide 26ml with separating funnel.Now start to regulate in pH=7 with 1:1 hydrochloric acid soln, react and obtain mixing thick product after 2 hours.
B product is purified: thick the mixing of step a product is heated with electric mantle, vacuumize simultaneously and carry out underpressure distillation.Residual solution to be evaporated is 1/2 o'clock of original solution volume, stops underpressure distillation.Pour in ready dehydrated alcohol solution into precipitating 3 times.Obtain white needle-like crystals, put into air dry oven continuous drying 73h under the environment of 60 DEG C, obtain white solid, be purer epoxy sodium succinate.
B. the preparation of poly-epoxy succinic acid product
Getting the epoxy sodium succinate that step b makes packs in there-necked flask, put into methyl-silicone oil and bathe heating, be raised to after 88 DEG C until temperature, start to add 1.5g calcium hydroxide initiator, divide and add for four times, add once every 5min, rear is that 40%NaOH regulates pH>12 by mass percent.Fully, after stirring reaction 2h, in the time that solution becomes the thick thing of light khaki color, stop heating.Secondly, product is put into acidifying alcohol solution and wash 3 times, leave standstill separatory, collect lower floor's thickness wax.Both obtained poly-epoxy succinic acid (PESA).
C. the preparation of poly-epoxy succinic acid derivative (being called for short Lcys-PESA)
The product of step B is put into there-necked flask, divide the Cys that adds 3.0g for 3 times, put into methyl-silicone oil and bathe heating, be raised to after 120 DEG C until temperature, start to regulate pH to 5, fully after stirring reaction 2.0h, stop heating, obtain Melon yellow look thick thing, dry under infrared drying lamp.Both poly-epoxy succinic acid derivative Lcys-PESA, airtight the saving backup of porphyrize 60 orders had been obtained.
Using method embodiment
Embodiment 1:
In 1 premium on currency, be made into respectively Lcys and 5mg/L self-control PESA and the 5mg/L Lcys compositional liquor of CSN-PESA, 10mg/L self-control PESA, the 10mg/L of Lcys-PESA, the 10mg/L of 10mg/L at volumetric flask according to mass concentration proportioning, then pour in Erlenmeyer flask, use with the plug of Glass tubing and cover tightly, measure the scale inhibition performance of medicament heat 10h in the water bath with thermostatic control of 80 DEG C after.The results are shown in Table 1.
Table 1
| Project | Scale inhibition performance/the % of resistance calcium carbonate scale |
| The Lcys-PESA of 10mg/L | 94.2 |
| The CSN-PESA of 10mg/L | 90.4 |
| 10mg/L makes PESA by oneself | 72.9 |
| The Lcys of 10mg/L | 40.5 |
| 5mg/L self-control PESA and 5mg/LLcys are composite | 60.4 |
Embodiment 2
In 1 premium on currency, be made into the scale inhibition liquid of the Lcys-PESA of 10mg/L and the CSN-PESA of 10mg/L according to mass concentration proportioning, the resistance calcium carbonate scale scale inhibition performance of measuring medicament after 10h is heated in the water bath with thermostatic control that is placed in respectively 60 DEG C, 65 DEG C, 70 DEG C, 75 DEG C, 80 DEG C and 85 DEG C.In temperature 60-85 DEG C situation, Scale inhibitors has good adaptability, and scale inhibition performance is more than 90%.Than effective with the poly-epoxy succinic acid (CSN-PESA) of thiocarbamide modification.Result as shown in Figure 1.
Embodiment 3
In 1 premium on currency, the scale inhibition liquid of the CSN-PESA of the Lcys-PESA that contains 10mg/L and 10mg/L, be mixed with respectively pH and be respectively 6.0,7.0,8.0,9.0,10.0, be then placed in the water bath with thermostatic control of 80 DEG C and heat the scale inhibition performance of measuring medicament after 10h.In the situation that pH is less than 10.0, the scale inhibition performance of Lcys-PESA Scale inhibitors all, more than 90%, higher than CSN-PESA, and also has superiority at biological degradability.Result as shown in Figure 2.
Embodiment 4:
Surface analysis by the present invention for calcium carbonate crystalline form
The crystal morphology of observing according to SEM, crystalline form that can qualitative definite calcium carbonate.Can find from stereoscan photograph, the CaCO3 crystal boundary that while not adding Scale inhibitors, Fig. 3 produces has square geometry clearly, and smooth surface, shape are regular, close structure.When adding poly-epoxy succinic acid derivative Scale inhibitors as less in the crystal formation size of the calcium carbonate of Fig. 4 generation, the more difficult appearance that is piled into fine and close crystal is to determine hard scale by the internal structure of itself, its size distribution is comparatively loose, and Lcys-PESA makes the crystal formation of calcium carbonate scale that distortion occur.Fig. 4 is compared with Fig. 5 (adding the poly-epoxy succinic acid of modification), and Lcys-PESA is obviously different from CSN-PESA.This is destructurized because of the original calcite of Lcys-PESA calcium carbonate, a lot of narrow scutellate crystallizations are formed, the variation of this structure may be that Scale inhibitors molecule embeds dirty sample granule interior, between the Surface Oxygen atom of the functional group of dirt dispersion agent and calcium carbonate, form hydrogen bond, cause the lattice distortion of particle, can make calcium carbonate scale layer become soft dirt from original hard scale, change the form of dirt layer, under the current scour of certain speed or the variation of temperature, the soft dirt of these slimings is than being easier to washed away draining, thereby scale inhibition performance improves.
Claims (4)
1. a poly-epoxy succinic acid derivative Scale inhibitors, the preparation method of this Scale inhibitors comprises the steps: cyclization and the purification of cyclisation product: it is epoxy sodium succinate that this step obtains white solid, the preparation of poly-epoxy succinic acid product: epoxy sodium succinate is packed in there-necked flask, put into methyl-silicone oil and bathe heating, be raised to after 80 DEG C-88 DEG C until temperature, starting to add calcium hydroxide initiator, add altogether calcium hydroxide initiator three to four times, is then that 40%NaOH regulates pH>12 by mass percent, fully after stirring reaction, product is put into acidifying alcohol solution and wash, leave standstill separatory, obtain poly-epoxy succinic acid PESA, it is characterized in that, also comprise the preparation of poly-epoxy succinic acid derivative Lcys-PESA, its preparation method is: the product of poly-epoxy succinic acid PESA is put into there-necked flask, divide the Cys that adds 1.5g-3.0g for 2-3 time, put into methyl-silicone oil and bathe heating, be raised to after 110 DEG C-120 DEG C until temperature, start to regulate pH between 4.0-6.0, fully after stirring reaction 2.5h-3.5h, when reaction system becomes orange-yellow thick thing, stop heating, after dry with drying installation, obtain Cys modified poly-epoxy succinic acid derivative Lcys-PESA, porphyrize is airtight to be saved backup.
2. poly-epoxy succinic acid derivative Scale inhibitors according to claim 1, is characterized in that: the molecular structural formula of described Cys is
。
3. poly-epoxy succinic acid derivative Scale inhibitors according to claim 1, is characterized in that: by weight, poly-epoxy succinic acid PESA and Cys ratio are 10:1.
4. poly-epoxy succinic acid derivative Scale inhibitors according to claim 1, is characterized in that: described drying installation is ultra red ray drying lamp.
5. poly-epoxy succinic acid derivative Scale inhibitors according to claim 1, is characterized in that: described Cys modified poly-epoxy succinic acid derivative Lcys-PESA finished product shredder is ground to 60 orders.
6. the application method of a poly-epoxy succinic acid derivative Scale inhibitors as claimed in claim 1, it is characterized in that, described poly-epoxy succinic acid derivative Scale inhibitors is 55 DEG C-85 DEG C in temperature, and pH value is 5.0～10.0, and scale inhibition performance is applied in the scope of 90%-98%.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103497321A (en) * | 2013-09-30 | 2014-01-08 | 宋晶冰 | Synthesis method of polyepoxysuccinic acid |
| CN105540878A (en) * | 2016-02-04 | 2016-05-04 | 江苏盛世水业有限公司 | Special scale and corrosion inhibitor for low-temperature water system |
| CN108658264B (en) * | 2018-04-17 | 2021-05-25 | 唐山师范学院 | Preparation and application method of multi-branched polyepoxysuccinic acid derivative scale and corrosion inhibitor |
| CN109516574B (en) * | 2018-11-23 | 2021-06-08 | 王建军 | Environment-friendly reverse osmosis scale inhibitor and preparation method thereof |
| CN111116889B (en) * | 2019-12-13 | 2022-08-09 | 河南清水源科技股份有限公司 | Method for preparing polyepoxysuccinic acid sodium by one-pot method |
| CN111848946B (en) * | 2020-07-30 | 2022-12-23 | 兰州交通大学 | Glutamine graft modified polyepoxysuccinic acid and preparation method and application thereof |
| CN111961146A (en) * | 2020-09-09 | 2020-11-20 | 中国石油天然气集团有限公司 | High-efficiency corrosion, low-corrosion, scale-inhibiting and environment-friendly acid liquor system and preparation method thereof |
| CN114956356B (en) * | 2022-06-09 | 2024-05-17 | 长江师范学院 | Mixed scale inhibitor and preparation method and application thereof |
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