CN103030215A - Micromolecule scale inhibitor and preparation method thereof - Google Patents
Micromolecule scale inhibitor and preparation method thereof Download PDFInfo
- Publication number
- CN103030215A CN103030215A CN2012105492766A CN201210549276A CN103030215A CN 103030215 A CN103030215 A CN 103030215A CN 2012105492766 A CN2012105492766 A CN 2012105492766A CN 201210549276 A CN201210549276 A CN 201210549276A CN 103030215 A CN103030215 A CN 103030215A
- Authority
- CN
- China
- Prior art keywords
- scale inhibitors
- mixture
- preparation
- conditions
- small molecule
- 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
- 0 CC(C)CC(CN*)N(*)C*CNC Chemical compound CC(C)CC(CN*)N(*)C*CNC 0.000 description 1
Images
Landscapes
- Detergent Compositions (AREA)
Abstract
The invention relates to a micromolecule scale inhibitor and a preparation method thereof. The micromolecule scale inhibitor has the molecular structure shown in the specification, wherein w is selected from 1,2 and 3; m is selected from 0 and 1; and n is selected from 1, 2 and 3. The preparation method comprises the following steps: using cyanuric chloride, amino dicarboxylic disodium, an amino compound and an acid-binding agent as the main raw materials; and synthesizing a compound comprising a polycarboxylic radical by utilizing substitution reaction difference of three chlorines in cyanuric chloride molecules. The compound is easy to dissolve in water, has strong metal ion chelation capacity under the alkalescent condition, can take good corrosion inhibition and scale inhibition effects and can be applied to the field of treatment on industrial cooling circulating water.
Description
Technical field
The invention belongs to catalyst preparation and water treatment field, be specifically related to small molecule Scale inhibitors and preparation method thereof.
Background technology
During modern industry was produced, in order to save cooling water, factory adopted cooling water circulation operation technique usually.Along with the increase of cooling water circulation number of times, the concentration of the difficulty soluble salts such as the calcium carbonate in the water coolant, calcium phosphate can substantially exceed its saturation solubility, separate out from water, and precipitation forms incrustation scale.The formation of incrustation scale can reduce the heat exchange efficiency of water cooler, even blocking pipeline, has a strong impact on the normal operation of production.
The Scale inhibitors that adds in the water coolant is the metal ions such as chelating, dispersion calcium, magnesium effectively, and the growth that slows down the indissoluble thing crystal such as calcium carbonate makes crystal remain on microcrystalline state, and then prevents the formation of incrustation scale.
The kind of Scale inhibitors is very abundant, according to development course and the functional group that plays a major role, roughly is divided into the natural polymer Scale inhibitors, contains Phosphorus Scale inhibitors, co-polymer Scale inhibitors and green new polymers Scale inhibitors.Wherein, the small molecules Scale inhibitors mainly is to contain Phosphorus Scale inhibitors, such as tripoly phosphate sodium STPP, Sodium hexametaphosphate 99, N, and N-dimethylated methene di 2 ethylhexyl phosphonic acid (DMMP), hydroxy ethylene diphosphonic acid (HEDP), ethylene diamine tetra methylene phosphonic acid (EDTMP) etc.But phosphorus containg substances can make body eutrophication, promotes phycomycete to grow, and brings environmental issue, and contained functional group is few in these phosphorous small molecules Scale inhibitorss, and scale inhibition effect is still waiting to improve.
The driven mechanics angle of Yang Baogui has studied and has optimized the reaction conditions of cyanuric chloride and aminocompound comparatively deeply, all sidedly, prepares multi-arm initiated core 2TDETA, 2TTETA, 2TTEPA, 3TDETA, 4TTETA and 5TTEPA.This research is for the invention provides reliable theoretical basis.
At present, the relevant report of synthetic poly carboxylic acid small molecules Scale inhibitors is comparatively rare take cyanuric chloride as raw material.
Summary of the invention
In order to overcome the shortcoming of above-mentioned prior art, the present invention aims to provide small molecule Scale inhibitors and preparation method thereof, and such Scale inhibitors is not phosphorous, can not make body eutrophication, and usage quantity is little, and high to the scale inhibition efficient of calcium carbonate, calcium phosphate etc.
In order to achieve the above object, the technical scheme taked of the present invention is:
The small molecule Scale inhibitors, its general structure is:
Wherein
The preparation method of small molecule Scale inhibitors may further comprise the steps:
1) in the four-hole boiling flask that agitator and thermometer are housed, adds 18.5～46.1 parts of mass fraction cyanuric chlorides and 30～60 portions of mass fraction frozen water, under 0～5 ℃ of condition, drip amino two carboxylic acid two sodium water solutions of 63.7～171.0 parts of mass fraction mass concentrations 30%, the acid binding agent aqueous solution with mass concentration 10% is regulated and hierarchy of control pH=5.5～6.5, add reactant afterreaction 2.5～4.0h, obtain mixture A, its main ingredient is intermediate I, and its general structure is:
M=0 wherein, 1; N=1,2,3;
2) mixture A is warming up to 35～45 ℃, drip the aminocompound aqueous solution of 10.0～31.6 parts of mass fraction mass concentrations 30%, the acid binding agent aqueous solution with mass concentration 10% is regulated and hierarchy of control pH=7.0～8.0, add reactant afterreaction 4.0～6.0h, obtain mixture B, its main ingredient is the intermediate II, and its general structure is:
Wherein
3) mixture B is warming up to 80～90 ℃, drip amino two carboxylic acid two sodium water solutions of 63.7～171.0 parts of mass fraction mass concentrations 30%, the acid binding agent aqueous solution with mass concentration 10% is regulated and hierarchy of control pH=7.0～8.0, add reactant afterreaction 2.5～4.0h, be cooled to room temperature and obtain mixture C;
4) with mixture C underpressure distillation 2～3 hours under vacuum tightness 0.1MPa and 55 ℃ of conditions, obtain dope D, with dope D vacuum-drying 4～6 hours under vacuum tightness 0.1MPa and 40 ℃ of conditions, obtain solid E, with anhydrous alcohol solution and remove by filter insolubles, after ethanol was removed in distillation under 0.1MPa, the 78.5 ℃ of conditions, vacuum-drying was 4～6 hours under vacuum tightness 0.1MPa and 40 ℃ of conditions with solid E, namely get pale yellow powder Scale inhibitors F, its general structure is:
Wherein
1，2，3；m=0，1；n=1，2，3
The two carboxylic acid disodiums of described amino are a kind of in 2 aminopentanedioic acid disodium (disodium glutamate), 3-aminoglutaric acid disodium and the AAA disodium.
Described aminocompound is a kind of in quadrol, diethylenetriamine, triethylene tetramine and the tetraethylene pentamine.
Described acid binding agent is a kind of in sodium hydroxide, yellow soda ash, salt of wormwood, the potassium hydroxide.
The present invention has the following advantages:
1. in the preparation process of small molecules Scale inhibitors disclosed by the invention, except dehydrated alcohol, need not to use other organic solvents, nontoxic, harmless; This type of Scale inhibitors is not phosphorous, can not make body eutrophication.
2. though the molecular weight of this type of Scale inhibitors is little, it contains more carboxylate radical, and usage quantity is little, and is high to the scale inhibition efficient of calcium carbonate, calcium phosphate etc.
Description of drawings
Accompanying drawing is the scale inhibition effect graphic representation of the embodiment of the invention one prepared Scale inhibitors.
Embodiment
Below by embodiment the present invention is specifically described, only be used for the present invention is further specified, can not be interpreted as limiting the scope of the invention.
Embodiment one
The preparation method of small molecule Scale inhibitors may further comprise the steps:
1) in the four-hole boiling flask that agitator and thermometer are housed, adds 27.6g cyanuric chloride and 40g frozen water, under 0～5 ℃ of condition, drip 2 aminopentanedioic acid two sodium water solutions of 95.6g mass concentration 30%, potential of hydrogen with the aqueous sodium hydroxide solution regulation system of mass concentration 10%, make the pH of system be controlled at 5.5～6.5, under 0～5 ℃ of condition, continue again reaction 2.5h after adding reactant, obtain mixture A;
2) mixture A is warming up to 35～40 ℃, drip the diethylenetriamine aqueous solution of 17.2g mass concentration 30%, potential of hydrogen with the aqueous sodium hydroxide solution regulation system of mass concentration 10%, make the pH of system be controlled at 7.0～8.0, under 35～40 ℃ of conditions, continue again reaction 4.0h after adding reactant, obtain mixture B;
3) mixture B is warming up to 80～85 ℃, drip 2 aminopentanedioic acid two sodium water solutions of 95.6g mass concentration 30%, potential of hydrogen with the aqueous sodium hydroxide solution regulation system of mass concentration 10%, make the pH of system be controlled at 7.0～8.0, under 80～85 ℃ of conditions, continue again reaction 2.5h after adding reactant, be cooled to room temperature, obtain mixture C;
4) with mixture C in vacuum tightness 0.1MPa and 55 ℃ of underpressure distillation 2h, obtain dope D, with dope D vacuum-drying 6h under vacuum tightness 0.1MPa and 40 ℃ of conditions, obtain solid E, with solid E with anhydrous alcohol solution and remove by filter insolubles, after ethanol was removed in distillation under 0.1MPa, the 78.5 ℃ of conditions, vacuum-drying 4h under vacuum tightness 0.1MPa and 40 ℃ of conditions namely got pale yellow powder Scale inhibitors F.
Embodiment two
The preparation method of small molecule Scale inhibitors may further comprise the steps:
1) in the four-hole boiling flask that agitator and thermometer are housed, adds 36.9g cyanuric chloride and 50g frozen water, under 0～5 ℃ of condition, drip 3-aminoglutaric acid two sodium water solutions of the mass concentration 30% of 127.4 parts of mass fractions, potential of hydrogen with the aqueous sodium carbonate regulation system of mass concentration 10%, make the pH of system be controlled at 5.5～6.5, under 0～5 ℃ of condition, continue reaction 3.0h after adding reactant, obtain mixture A
2) mixture A is warming up to 40～45 ℃, drip the triethylene tetramine aqueous solution of 24.3g mass concentration 30%, potential of hydrogen with the aqueous sodium carbonate regulation system of mass concentration 10%, make the pH of system be controlled at 7.0～8.0, under 40～45 ℃ of conditions, continue reaction 5.0h after adding reactant, obtain mixture B;
3) mixture B is warming up to 85～90 ℃, drip 3-aminoglutaric acid two sodium water solutions of 127.4g mass concentration 30%, potential of hydrogen with the aqueous sodium carbonate regulation system of mass concentration 10%, make the pH of system be controlled at 7.0～8.0, under 85～90 ℃ of conditions, continue 3.0h after adding reactant, be cooled to room temperature, obtain mixture C;
4) with mixture C in vacuum tightness 0.1MPa and 55 ℃ of underpressure distillation 2.5h, obtain dope D, with dope D vacuum-drying 6h under vacuum tightness 0.1MPa and 40 ℃ of conditions, obtain solid E, with solid E with anhydrous alcohol solution and remove by filter insolubles, after ethanol was removed in distillation under 0.1MPa, the 78.5 ℃ of conditions, vacuum-drying 5h under vacuum tightness 0.1MPa and 40 ℃ of conditions namely got pale yellow powder Scale inhibitors F.
Embodiment three
The preparation method of small molecule Scale inhibitors may further comprise the steps:
1) in the four-hole boiling flask that agitator and thermometer are housed, adds 46.1g cyanuric chloride and 60g frozen water, under 0～5 ℃ of condition, drip AAA two sodium water solutions of 171.0g mass concentration 30%, potential of hydrogen with the wet chemical regulation system of mass concentration 10%, make the pH of system be controlled at 5.5～6.5, under 0～5 ℃ of condition, continue reaction 4.0h after adding reactant, obtain mixture A;
2) mixture A is warming up to 40～45 ℃, drip the tetraethylene pentamine aqueous solution of 31.6g mass concentration 30%, potential of hydrogen with the wet chemical regulation system of mass concentration 10%, make the pH of system be controlled at 7.0～8.0, under 40～45 ℃ of conditions, continue reaction 6.0h after adding reactant, obtain mixture B;
3) mixture B is warming up to 85～90 ℃, drip AAA two sodium water solutions of 171.0g mass concentration 30%, potential of hydrogen with the wet chemical regulation system of mass concentration 10%, make the pH of system be controlled at 7.0～8.0, under 85～90 ℃ of conditions, continue reaction 4.0h after adding reactant, be cooled to room temperature, obtain mixture C;
4) with mixture C in vacuum tightness 0.1MPa and 55 ℃ of underpressure distillation 3h, obtain dope D, with dope D vacuum-drying 6h under vacuum tightness 0.1MPa and 40 ℃ of conditions, obtain solid E, with solid E with anhydrous alcohol solution and remove by filter insolubles, after ethanol was removed in distillation under 0.1MPa, the 78.5 ℃ of conditions, vacuum-drying 6h under vacuum tightness 0.1MPa and 40 ℃ of conditions namely got pale yellow powder Scale inhibitors F.
Embodiment four
The preparation method of small molecule Scale inhibitors may further comprise the steps:
1) in the four-hole boiling flask that agitator and thermometer are housed, adds 18.5g cyanuric chloride and 30g frozen water, under 0～5 ℃ of condition, drip 2 aminopentanedioic acid two sodium water solutions of 63.9g mass concentration 30%, and the while slowly drips the potential of hydrogen of the potassium hydroxide aqueous solution regulation system of mass concentration 10%, make the pH of system be controlled at 5.5～6.5, under 0～5 ℃ of condition, continue reaction 2.5h after adding reactant, obtain mixture A;
2) mixture A is warming up to 35～40 ℃, drip the ethylenediamine solution of 10g mass concentration 30%, potential of hydrogen with the potassium hydroxide aqueous solution regulation system of mass concentration 10%, make the pH of system be controlled at 7.0～8.0, under 35～40 ℃ of conditions, continue reaction 4.0h after adding reactant, obtain mixture B;
3) mixture B is warming up to 80～85 ℃, drip 2 aminopentanedioic acid two sodium water solutions of 63.7g mass concentration 30%, potential of hydrogen with the potassium hydroxide aqueous solution regulation system of mass concentration 10%, make the pH of system be controlled at 7.0～8.0, under 80～85 ℃ of conditions, continue reaction 2.5h after adding reactant, be cooled to room temperature, obtain mixture C;
4) with mixture C in vacuum tightness 0.1MPa and 55 ℃ of underpressure distillation 2h, obtain dope D, with dope D vacuum-drying 4h under vacuum tightness 0.1MPa and 40 ℃ of conditions, obtain solid E, with solid E with anhydrous alcohol solution and remove by filter insolubles, after a large amount of ethanol were removed in distillation under 0.1MPa, the 78.5 ℃ of conditions, vacuum-drying 4h under vacuum tightness 0.1MPa and 40 ℃ of conditions namely got pale yellow powder Scale inhibitors F.
The scale-inhibiting properties test
Take embodiment one prepared Scale inhibitors as example, carry out the scale inhibition experiment with reference to State Standard of the People's Republic of China GB/T16632-2008 water conditioner scale-inhibiting properties mensuration-tosca method.The scale inhibition requirement of experiment of calcium phosphate and method can be carried out with reference to the company standard Q/SY TZ 0177-2007 of PetroChina Company Ltd..
1. calcium carbonate scale inhibition experiment condition: c (Ca
2+)=240mg/L, c (HCO
3 -)=732mg/L, T=80 ℃, t=10h.With this understanding, when the concentration of Scale inhibitors was 6mg/L, its scale inhibition performance to calcium carbonate had reached 90.1%, as shown in drawings.
2. calcium phosphate scale inhibition experiment condition: c (Ca
2+)=250mg/L, c (PO
4 3-)=5mg/L, T=80 ℃, t=10h.With this understanding, when the concentration of Scale inhibitors sample was 7mg/L, its scale inhibition performance to calcium carbonate had reached 90.6%, as shown in drawings.
Claims (5)
1. the small molecule Scale inhibitors is characterized in that, general structure is:
Wherein
2. small molecule Scale inhibitors according to claim 1 is characterized in that the preparation method may further comprise the steps:
1) in the four-hole boiling flask that agitator and thermometer are housed, adds 18.5～46.1 parts of mass fraction cyanuric chlorides and 30～60 portions of mass fraction frozen water, under 0～5 ℃ of condition, drip amino two carboxylic acid two sodium water solutions of 63.7～171.0 parts of mass fraction mass concentrations 30%, the acid binding agent aqueous solution with mass concentration 10% is regulated and hierarchy of control pH=5.5～6.5, add reactant afterreaction 2.5～4.0h, obtain mixture A;
2) mixture A is warming up to 35～45 ℃, drip the aminocompound aqueous solution of 10.0～31.6 parts of mass fraction mass concentrations 30%, the acid binding agent aqueous solution with mass concentration 10% is regulated and hierarchy of control pH=7.0～8.0, adds reactant afterreaction 4.0～6.0h, obtains mixture B;
3) mixture B is warming up to 80～90 ℃, drip amino two carboxylic acid two sodium water solutions of 63.7～171.0 parts of mass fraction mass concentrations 30%, the acid binding agent aqueous solution with mass concentration 10% is regulated and hierarchy of control pH=7.0～8.0, add reactant afterreaction 2.5～4.0h, be cooled to room temperature and obtain mixture C;
4) with mixture C underpressure distillation 2～3 hours under vacuum tightness 0.1MPa and 55 ℃ of conditions, obtain dope D, with dope D vacuum-drying 4～6 hours under vacuum tightness 0.1MPa and 40 ℃ of conditions, obtain solid E, with anhydrous alcohol solution and remove by filter insolubles, after ethanol was removed in distillation under 0.1MPa, the 78.5 ℃ of conditions, vacuum-drying was 4～6 hours under vacuum tightness 0.1MPa and 40 ℃ of conditions with solid E, namely get pale yellow powder Scale inhibitors F, its general structure is:
Wherein
3. the preparation method of small molecule Scale inhibitors according to claim 2 is characterized in that: the two carboxylic acid disodiums of described amino are a kind of in 2 aminopentanedioic acid disodium (disodium glutamate), 3-aminoglutaric acid disodium and the AAA disodium.
4. the preparation method of small molecule Scale inhibitors according to claim 2 is characterized in that: described aminocompound is a kind of in quadrol, diethylenetriamine, triethylene tetramine and the tetraethylene pentamine.
5. the preparation method of small molecule Scale inhibitors according to claim 2 is characterized in that: described acid binding agent is a kind of in sodium hydroxide, yellow soda ash, salt of wormwood, the potassium hydroxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012105492766A CN103030215A (en) | 2012-12-17 | 2012-12-17 | Micromolecule scale inhibitor and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012105492766A CN103030215A (en) | 2012-12-17 | 2012-12-17 | Micromolecule scale inhibitor and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103030215A true CN103030215A (en) | 2013-04-10 |
Family
ID=48017674
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012105492766A Pending CN103030215A (en) | 2012-12-17 | 2012-12-17 | Micromolecule scale inhibitor and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103030215A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5414095A (en) * | 1994-01-03 | 1995-05-09 | The Sherwin-Williams Company | Anhydride-functional primary alkyl halides |
| CN102764610A (en) * | 2012-07-05 | 2012-11-07 | 陕西科技大学 | Chelating surfactants containing triazine rings and preparation method thereof |
-
2012
- 2012-12-17 CN CN2012105492766A patent/CN103030215A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5414095A (en) * | 1994-01-03 | 1995-05-09 | The Sherwin-Williams Company | Anhydride-functional primary alkyl halides |
| CN102764610A (en) * | 2012-07-05 | 2012-11-07 | 陕西科技大学 | Chelating surfactants containing triazine rings and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103265696B (en) | Dendrimer with pentaerythritol core terminal and phosphonic acid terminal group, preparation method and uses thereof | |
| JP7334356B2 (en) | Lithium extraction method | |
| US9242863B2 (en) | Process and reagents for the inhibition or reduction of scale formation during phosphoric acid production | |
| CN101700937B (en) | Composite scale inhibitor | |
| EP2990379B1 (en) | Process and reagents for the inhibition or reduction of scale formation during phosphoric acid production | |
| MX2013010468A (en) | Preventing or reducing scale in wet-process phosphoric acid production. | |
| US20160318763A1 (en) | Methods and compositions for chemical drying and producing struvite | |
| CN103998633A (en) | Method for extraction of lithium from lithium bearing solution | |
| CN105565513A (en) | Composite corrosion and scale inhibitor and its preparation method and use | |
| CN101962233A (en) | Dendritic polymer and sodium polyaspartate compound scale inhibitor for inhibiting silicon scale deposition in water | |
| CN103254428B (en) | Trimethylolpropane dendritic polymer with nuclear-end phosphonic acid end group as well as preparation method and application for same | |
| CN109231509A (en) | A kind of scale inhibitor for salt manufacture and its application | |
| CN103030215A (en) | Micromolecule scale inhibitor and preparation method thereof | |
| CN103739096A (en) | Corrosion and scale inhibitor for boiler | |
| CN110937700A (en) | Corrosion and scale inhibitor for circulating cooling water system and preparation method thereof | |
| CN104478104A (en) | Phosphorus-free solid scale inhibitor and using method thereof | |
| CN101863561B (en) | Superhigh-temperature circulating water antisludging agent and application thereof | |
| CN101549347A (en) | A scale inhibiting method of extraction apparatus in the wet phosphoric acid purifying process | |
| CN102993071A (en) | Method for synthesizing corrosion and scale inhibitor S-carboxyalkylthiosuccinic acid by adopting one-step method | |
| CN105585143A (en) | Scale inhibitor for industrial water treatment and preparation method and application method thereof | |
| CN106830375B (en) | Scale inhibitor for hot water boiler and application method thereof | |
| CN113087903A (en) | High-temperature-resistant modified polyaspartic acid scale inhibitor and preparation method and use method thereof | |
| CN104556424A (en) | High-hardness high-alkalinity phosphorus-free scale and corrosion inhibitor and preparation method thereof | |
| CN104692546B (en) | A kind of demineralized water water treatment agent and its preparation method and application | |
| CN105417766B (en) | A kind of ammonia exchanges the Crystallization Separation method of ammonia nitrogen in waste water |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20130410 |