CN103086524A - High-efficiency grey water dispersing agent - Google Patents
High-efficiency grey water dispersing agent Download PDFInfo
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- CN103086524A CN103086524A CN2012105205140A CN201210520514A CN103086524A CN 103086524 A CN103086524 A CN 103086524A CN 2012105205140 A CN2012105205140 A CN 2012105205140A CN 201210520514 A CN201210520514 A CN 201210520514A CN 103086524 A CN103086524 A CN 103086524A
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Abstract
The invention relates to a high-efficiency grey water dispersing agent which is a composition consisting of 40-60 percent of acrylic acid-2-polyscrylide-2-methyl acrylsulfonate, 15-35 percent of 2-phosphate-1,2,4-tricarboxylic acid butane, 5-25 percent of amino trimethylene phosphonic acid, 5-15 percent of hydroxyethylidene-1,1-diphosphonic acid and 5-15 percent of hydrolytic polymaleic anhydride. The dispersing agent is stable in property under the conditions of 40MPa and 250 DEG C, has a high dispersing capacity at the high temperature of 300 DEG C, has a good dispersing function on high-basicity, high-hardness, high-PH value and high ash content and high concentration multiple under the required high-concentration times in a water-coal-slurry pressurization and gasification device, can effectively delay the scale forming tendency and is applicable to a circulating cooling water system in industries such as power, metallurgy and papermaking. The addition in a water system is determined according to the water quality and working conditions, and the amount is 50-80mg/l according to the flow sum of a low-pressure grey water pump and a high-pressure grey water pump.
Description
Technical field
The present invention relates to the dispersion agent that a kind of Coal Chemical Industry, industrial circulate water good antiscale property are used, be specifically related to a kind of efficient grey water dispersant.
Background technology
In the Coal Chemical Industry industry, the coal water slurry gasification gas-making process, owing to having used the coal ash that fusing point is high, for reducing the ash fusion point of coal, has added fusing assistant CaCO
3, CaCO
3at high temperature decompose and generate CaO, the SiO in partial CaO and coal
2, Al
2o
3deng reaction, reduced the ash fusion point of coal, remaining CaO is dissolved in Coal-gas Washing Water Using, has greatly increased the calcium in the Coal-gas Washing Water Using firmly and basicity, make buck become the serious scale type water quality of high rigidity, high alkalinity, high pH value, cause the ash water system serious scale.In addition buck before entering vapourizing furnace and venturi scrubber, washing tower, to heat up, supercharging, this has more increased the difficulty of buck scale inhibition, dispersion treatment, serious fouling often makes device continuous operation very short time just need the stopping production scale removal, has a strong impact on the normal operation of equipment.
For the hardness that guarantees buck, the requirement that basicity reaches regulation, the normal operation of assurance equipment, both at home and abroad the treatment agent of Coal Chemical Engineering Industry cycling use of water conducted in-depth research, from chromium system, phosphorus system, molybdenum system early, arrive again the treatment agent of organic phosphine acids, but, because the compound itself containing chromium, phosphorus etc. in chromium system, phosphorus system, molybdenum system just has certain harm to human body, as the chromic salt of sexavalence, nitrite etc. are toxic substances, thereby apply and be very limited, the problems such as the corrosion when treatment agent energy resolution system of organic phosphine acids moves and calcium carbonate scaling, but under harsh condition of water quality, only with organic phosphine acids treatment agent, can't complete water conditioning, a kind of stable form corrosion inhibiting and descaling agent as disclosed as patent 200410025673.9, contain Amino Trimethylene Phosphonic Acid, ethylenediamine tetramethylene phosphonic acid, amino ethylidine di 2 ethylhexyl phosphonic acid, zinc sulfate and water, it is the composite Scale inhibitors of a kind of organic phospho acid and inorganic salt, Amino Trimethylene Phosphonic Acid when processing buck, ethylenediamine tetramethylene phosphonic acid, the large usage quantity of amino ethylidine di 2 ethylhexyl phosphonic acid, but have a large amount of P contained compound discharges simultaneously, form new pollution, unnecessary zinc salt also can affect, the copolymer analog dirt dispersion agent is the New Type Water Treatment Chemicals of developing in recent years, its without phosphorus formula can not cause secondary pollution, but its individual curing effect is unsatisfactory, large usage quantity and price are higher, uneconomical, therefore its often with other treatment agent compound use, polymer grey-water stabilizer as disclosed as patent 200610083815.6, co-polymer of sulfonate, Amino Trimethylene Phosphonic Acid, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid, the composite use of polymaleic anhydride have been adopted, but due to kind and the content Incomplete matching of constituent, so undesirable to the processing of some harsh water quality.Therefore a kind ofly can effectively stop fouling tendency in all kinds of ash water systems, slow down Scale inhibitors and ash water system to the corrosion of pipeline, can not form new pollution again, economic grey water dispersant has become the active demand of Coal Chemical Industry industry again simultaneously.
Summary of the invention
The present invention is in order to address the above problem, provide under a kind of, high alkalinity hard at high temperature, high pressure, high calcium and high ash content condition and there is stability and good distribution effect, particularly the silicate of calcium in buck and aluminate etc. and admittedly outstanding thing are had to good dissemination, can stop fouling tendency in ash water system and the ash water system efficient grey water dispersant to the corrosive nature of pipeline.
Technical scheme of the present invention is: a kind of efficient grey water dispersant comprises following component by weight:
Vinylformic acid-2-acrylamide-2-methyl propane sulfonic (AA/AMPS) 40-60 part
2-phosphate-1,2,4-butane tricarboxylate (PBTCA) 15-35 part
Amino Trimethylene Phosphonic Acid (ATMP) 5-25 part
Hydroxy ethylene diphosphonic acid (HEDP) 5-15 part
Hydrolytic polymaleic anhydride (PHMA) 5-15 part.
Further, a kind of efficient grey water dispersant preferably includes following component by weight:
Vinylformic acid-2-acrylamide-2-methyl propane sulfonic (AA/AMPS) 45-55 part
2-phosphate-1,2,4-butane tricarboxylate (PBTCA) 20-30 part
Amino Trimethylene Phosphonic Acid (ATMP) 10-20 part
Hydroxy ethylene diphosphonic acid (HEDP) 5-10 part
Hydrolytic polymaleic anhydride (PHMA) 5-10 part.
Again further, a kind of efficient grey water dispersant, the best comprises following component by weight:
Vinylformic acid-50 parts of 2-acrylamide-2-methyl propane sulfonics (AA/AMPS)
2-phosphate-1,2,25 parts of 4-butane tricarboxylates (PBTCA)
15 parts of Amino Trimethylene Phosphonic Acid (ATMP)
5 parts of hydroxy ethylene diphosphonic acids (HEDP)
5 parts of hydrolytic polymaleic anhydride (PHMA).
The invention has the beneficial effects as follows:
(1) at first the present invention acts synergistically with the treatment effect under harsh condition of water quality by polycomponent, and the effect of each component is as follows:
Described vinylformic acid-2-acrylamide-2-methyl propane sulfonic is to be formed in processing the poor desired ratio copolymerization of buck by vinylformic acid and 2-acrylamide-2-methyl propane sulfonic, its sulfonic group acidity is stronger, effectively prevented from reacting with the water intermediate ion due to the slightly water-wet multipolymer and generated that the insoluble material--the calcium gel particularly has restraining effect preferably to calcium phosphate scale, the carboxylic acid group is a kind of weak acid base, and scale inhibition and dispersion performance is good, is resistance CaCO
3, CaSO
4the main functional group of dirt, have significant scale effect to the calcium phosphate in water, calcium carbonate, zinc dirt etc., especially calcium phosphate had to unique restraining effect, and hydroxyl, amide group etc. are to resistance Ca
3(PO
4)
2dirt is useful, therefore vinylformic acid-2-acrylamide-2-methyl propane sulfonic is the polymer water treatment agent that simultaneously has strong acid and two kinds of functional groups of weak acid, good resistance calcium carbonate and calcium phosphate scale effect are not only arranged, also there is extremely strong corrosion inhibiting ability and dissemination, excellent high temperature resistant and antioxidant property, disperse iron in alkaline aqueous solution, the oxyhydroxide of zinc and the excellent property of calcium phosphate, and there is certain sequestering action, nontoxic to environment, pollution-free, during with the composite use of organic phosphine (the present invention is added is Amino Trimethylene Phosphonic Acid and hydroxy ethylene diphosphonic acid), the scale effect increase is very obvious, simultaneously, vinylformic acid-2-acrylamide-2-methyl propane sulfonic can also prevent the deposition of ferric oxide at the duct wall of ash water system, play certain corrosion inhibition.
2-phosphate-1,2, the 4-butane tricarboxylate is a kind of low-phosphorus corrosion and scale inhibitor, because it has the structural performance of phosphonic acids and carboxylic acid, has good scale inhibition and corrosion inhibition, especially calcium carbonate scale and calcium phosphate scale; Zine ion etc. is had to unique stable effect, stoped the generation of zinc dirt, in ash water system, the performance of its resistance calcium carbonate, calcium phosphate scale has further been strengthened again in the increase of zinc ion concentration simultaneously.
(2) Synergistic Mechanisms and the advantage between each component in efficient grey water dispersant
2-phosphate-1, 2, when the 4-butane tricarboxylate uses as corrosion inhibiting and descaling agent separately, required dosage is larger, can discharge relatively large P contained compound, but the discharge of P contained compound easily pollutes water body, China GB8979-1996 has stipulated that the first grade discharging of phosphorus requires (in P)≤0.5mg/L, and both jointly brought into play its scale-inhibiting properties after itself and the composite use of multipolymer (the present invention is added is vinylformic acid-2-acrylamide-2-methyl propane sulfonic), additive capacity all can greatly reduce, can bring into play again its efficient scale inhibitor effect when meeting national grade one discharge standard fully.
Amino Trimethylene Phosphonic Acid is stable chemical nature in water, and facile hydrolysis not easily generates stable inner complex with many kinds of metal ions especially zine ion in water, plays the effect of minimizing hardware or corrosion of piping; Simultaneously, having good lower bound suppresses and the lattice distortion effect, can stop the formation of incrustation scale, particularly calcium carbonate scale that in water, the scaling salt class forms, but it can discharge P contained compound equally, and experiment confirms, with the composite use of poly carboxylic acid (it is hydrolytic polymaleic anhydride that the present invention adds), strengthened the scale-inhibiting properties of its unit product, reduced consumption, suppressed the discharge of P contained compound, can bring into play again its efficient resistive energy when meeting national grade one discharge standard fully.
A kind of organophosphorus acids of hydroxy ethylene diphosphonic acid anti-incrustation corrosion inhibitor, the main generation that suppresses calcium carbonate scale, still very stable under high PH, facile hydrolysis not, can with water in metal ion, especially calcium ion formation six-membered ring chelate, thereby tool is scale inhibition effect the obvious threshold effect of tool preferably, shows desirable synergistic effect when with other water conditioner compound uses.When cause is made inhibiter separately, aequum is higher, and with the composite use of organic phosphonate (this product is added is Amino Trimethylene Phosphonic Acid), can reduce its usage quantity, reach satisfied corrosion mitigating effect simultaneously, they can form stable complex compound with many kinds of metal ions such as iron, copper, zinc, oxide compound that can the dissolution of metals surface also generates stable complex compound and is attached to densely metallic surface, play the effect of inhibition to prevent metal from further oxidation occurring when the high temperature, still can play good corrosion-mitigation scale-inhibition effect under 250 ℃.
(3) efficient grey water dispersant product has solved the processing difficult problem of harsh water quality, at 40MPa, under 250 ℃ of conditions, character is still very stable, still there is good dispersive ability when the high temperature of 300 ℃, to high-alkali, high hard, high pH value, the buck of ash-rich has dissemination preferably, can effectively delay its fouling tendency, be particularly suitable for coal gasification apparatus Heisui River/ash water system high temperature, high pH, high alkalinity, the requirement of high rigidity to the medicament property, it is the optimal dirt dispersion agent of realizing the high concentration multiple operation, can be widely used in electric power, the recirculating cooling water system of the industries such as metallurgy and papermaking, the present invention at the dosage of water system depending on water quality and operating mode, consumption is that 50～80mg/l(is by low pressure ash water pump and high pressure ash pump capacity summation).
To sum up, the efficient grey water dispersant that one group of full-inorganic that the present invention screen and develops according to synthetic, the mechanism of action and the mutual Synergistic Mechanisms of organic water treatment agent is filled a prescription, buck in the coal water slurry gasification gas-making process and other sewage are all had to good treatment effect, guaranteed the normal operation of equipment, maintenance of the equipment and production cost have been reduced, water body after efficient grey water dispersant is processed can reach the requirement of national GB8979-1996 simultaneously, has avoided the secondary pollution to environment.
Embodiment
Test, the method for inspection below in conjunction with embodiment and relevant national standard regulation are described further effect of the present invention.
Vinylformic acid used in the present invention-2-acrylamide-2-methyl propane sulfonic (the lower AA/AMPS that is called for short), 2-phosphate-1; 2,4-butane tricarboxylate (the lower PBTCA of abbreviation), Amino Trimethylene Phosphonic Acid (the lower ATMP of abbreviation), hydroxy ethylene diphosphonic acid (the lower HEDP of abbreviation), hydrolytic polymaleic anhydride (the lower HPMA that is called for short) provide by Jiangsu Jiang Hai chemical industry.
Table 1 has been enumerated the efficient grey water dispersant be comprised of the different content component:
Efficient grey water dispersant prepared by above-described embodiment, carried out quick scale-inhibiting properties test according to standard HG/T2024-2009 " mensuration of water conditioner scale-inhibiting properties--Bubbling method "; And carried out the test of rotary hanging plate Determination of Corrosion Property according to " rotary hanging plate weight-loss method " in " water coolant analysis and the test method " of the establishment of prodution and development section of China Petroleum Chemicals Corporation, various test situation are as follows:
(1) quick scale-inhibiting properties testing experiment (pressing HG/T2024-2009)
Test sample: the efficient grey water dispersant of the present invention;
Test apparatus and equipment: KZC-1 type scale-inhibiting properties tester, the market sale commodity, produced by Gaoyou City, Jiangsu Province skyscraping Electron equipment Co., Ltd; Drop-burette (acid): 100ml, 500ml;
The preparation of test solution: with drop-burette (5.2), add sodium hydrogen carbonate solution (4.7) a
2mL, in the 500mL volumetric flask, moves into 5.00mL water conditioner sample solution (6.1), adds 250mL water, shakes up.Slowly add calcium chloride solution (4.9) a with drop-burette (5.2)
3mL, be diluted with water to scale, shakes up, and is prepared in 1L and contains 5.00mg water treatment agent, 240mg (6.00mmol) calcium ion (Ca
2+) and 732mg (12.0mmol) bicarbonate ion (HCO
3 -) test solution;
Reagent: 1. potassium hydroxide solution: 200g/L, 2. disodium ethylene diamine tetraacetate (EDTA): 0.01mol/L, 3. hydrochloric acid: 0.1mol/L, 4. calcein-phenolphthalein mixture indicator: take the 0.20g fluorexon, 0.070g phenolphthalein (GB 10729), be placed in glass mortar, adds Repone K (GB 646) porphyrize of 20g after 120 ℃ of oven dry to mix, and stores in brown port grinding bottle, 5. tetrabromo-mcresolsulfonphthalein-methyl red mixture indicator: 3 volume 1.00g/L tetrabromo-mcresolsulfonphthalein (HG3-1220) ethanolic solns mix with 1 volume 2.00g/L methyl red (HG3-958) ethanolic soln, 6. sodium hydrogen carbonate solution: about 25.3g/L solution, preparation: take 25.3g sodium bicarbonate (4.6) in the 100mL beaker, use water dissolution, quantitatively be transferred in the 10000mL volumetric flask, be diluted with water to scale, shake up, demarcate: pipette in sodium hydrogen carbonate solution 5.00mL and 250mL Erlenmeyer flask, add about 50mL water, 4 tetrabromo-mcresolsulfonphthalein-methyl red mixture indicators (4.5), be titrated to solution with Hydrochloric Standard Titration (4.3) and be terminal by the light blue lilac that sports, write down the volume V of consumed Hydrochloric Standard Titration (4.3)
1, 7. calcium chloride solution: about 16.7g/L solution, preparation: take 16.7g Calcium Chloride Powder Anhydrous (4.8) in the 1000mL beaker, use water dissolution, quantitatively be transferred in the 10000mL volumetric flask, be diluted with water to scale, shake up, demarcate: take in 2.000mL calcium chloride solution 2500mL Erlenmeyer flask, add about 800mL water 50mL potassium hydroxide solution (4.1), about 30mg calcein-phenolphthalein mixture indicator (4.4), under black background, pipette that yellow-green fluorescence that EDTA standard titration solution (4.2) is titrated to solution suddenly disappears and while redness occurring with drop-burette (5.2), be terminal, write down the volume V of consumed EDTA standard titration solution (4.2)
2,
Scale-inhibiting properties is measured: measure about 450mL test solution (7.1) in the 500mL three-necked flask, by in the water bath with thermostatic control of 60 ± 0.2 ℃ of this flask immersions, by (5.1), install, simultaneously, blast air with the flow of 80L/h, after 6h, stop blasting air, take out three-necked flask, put to room temperature, this solution is calcium ion steady concentration solution.Pipette this solution of 25.00mL in the 250mL Erlenmeyer flask, add about 80mL water.Except using 10mL drop-burette (5.3) instead, by the method for demarcating calcium chloride solution, measure the steady concentration of calcium ion, write down the volume V of consumed EDTA standard titration solution (4.2)
3.
The scale-inhibiting properties testing experiment the results are shown in Table 2 fast
The quick scale-inhibiting properties test-results of the efficient grey water dispersant of table 2 the present invention table
From table 2, the quick scale-inhibiting properties test of the efficient grey water dispersant of embodiment 1～10 resistance calcium carbonate rate all can reach more than 85%.
(2) rotary hanging plate Determination of Corrosion Property test
Test sample: the efficient grey water dispersant of the present invention;
Lacing film: copper pipe, specification is φ 20 * 1mm * 10mm, commercially available;
Instrument and equipment: 2L beaker; RCC-III type spin etching hanging test instrument, produced by Gaoyou City, Jiangsu Province skyscraping Electron equipment Co., Ltd;
Test water: tap water;
Test method: by 5～No. 50 sand papering polishings for lacing film, with the dehydrated alcohol degreasing and clean up, moisture eliminator inner drying 24 hours, weigh, measure its surface-area, the test water sample prepared is added in the 2L beaker, the test piece of two identical materials is hung wherein, the test medicine (by product) that adds the efficient grey water dispersant 8mg/L of the present invention, start instrument, test piece rotating speed 75-150 rev/min, the heap experimental water is heated and remains on 45 ± 1 ℃, every 4 hours supplementary test water samples once, make the page remain at scale marks, reach 72 hours when runtime, stopping test piece rotating, the taking-up test piece is observed, and with vulcanite to the test piece wiping, clean, after drying, weigh, calculate its uniform corrosion rate, do the blank test simultaneously.Uniform corrosion rate calculates according to the following formula:
In formula, V is uniform corrosion rate (mm/a), and W is the front test piece quality (g) of test, W
0for testing rear test piece quality (g), the surface-area (cm that A is test piece
2), the density (g/cm that ρ is test piece
3), t is time (h), and 8760 is the hours (h/a) suitable with a year, and 10 is the millimeter that 1cm is suitable (mm/cm).Experimental result is in Table 3.
The efficient grey water dispersant rotary hanging plate Determination of Corrosion Property of table 3 the present invention is table as a result
From table 3, embodiment 1～10 rotary hanging plate corrosive nature test experiments result shows, the erosion rate of lacing film all is less than the erosion rate 0.005mm/a standard of GB50050-2007 regulation.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any modifications of doing within the spirit and principles in the present invention, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (3)
1. an efficient grey water dispersant comprises following component by weight:
Vinylformic acid-2-acrylamide-2-methyl propane sulfonic 40-60 part
2-phosphate-1,2,4-butane tricarboxylate 15-35 part
Amino Trimethylene Phosphonic Acid 5-25 part
Hydroxy ethylene diphosphonic acid 5-15 part
Hydrolytic polymaleic anhydride 5-15 part.
2. efficient grey water dispersant according to claim 1 comprises following component by weight:
Vinylformic acid-2-acrylamide-2-methyl propane sulfonic 45-55 part
2-phosphate-1,2,4-butane tricarboxylate 20-30 part
Amino Trimethylene Phosphonic Acid 10-20 part
Hydroxy ethylene diphosphonic acid 5-10 part
Hydrolytic polymaleic anhydride 5-10 part.
3. efficient grey water dispersant according to claim 1 and 2 comprises following component by weight:
Vinylformic acid-50 parts of 2-acrylamide-2-methyl propane sulfonics
2-phosphate-1,2,25 parts of 4-butane tricarboxylates
15 parts of Amino Trimethylene Phosphonic Acid
5 parts of hydroxy ethylene diphosphonic acids
5 parts of hydrolytic polymaleic anhydride.
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| CN103708632A (en) * | 2014-01-13 | 2014-04-09 | 湖南东盈煤化工技术开发有限公司 | Grey water antiscale dispersion agent for gasification |
| CN104291455A (en) * | 2014-08-29 | 2015-01-21 | 厦门紫金矿冶技术有限公司 | Composite multi-element mine scale inhibition and dispersion agent and application thereof |
| CN105754670A (en) * | 2016-04-06 | 2016-07-13 | 山东泰和水处理科技股份有限公司 | Coal water slurry dispersion stabilizer |
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| CN103708632A (en) * | 2014-01-13 | 2014-04-09 | 湖南东盈煤化工技术开发有限公司 | Grey water antiscale dispersion agent for gasification |
| CN104291455A (en) * | 2014-08-29 | 2015-01-21 | 厦门紫金矿冶技术有限公司 | Composite multi-element mine scale inhibition and dispersion agent and application thereof |
| CN104291455B (en) * | 2014-08-29 | 2016-02-24 | 厦门紫金矿冶技术有限公司 | A kind of composite multi-component mine dirt dispersion agent and application thereof |
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| CN106830378A (en) * | 2017-02-23 | 2017-06-13 | 山东化友水处理技术有限公司 | A kind of buck scale preventative and its preparation and filler test method |
| CN107021566A (en) * | 2017-04-10 | 2017-08-08 | 南京工大开元环保科技（滁州）有限公司 | Efficient low-phosphorus high temperature buck dispersant preparation method and its application |
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| CN109650567A (en) * | 2019-01-31 | 2019-04-19 | 陈建华 | Gravity die Grey water antiscale dispersion agent and application adaptively drop in a kind of coal gasification grey black water |
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| CN113816504A (en) * | 2021-09-24 | 2021-12-21 | 南京开广化工有限公司 | Coal gasification ash water dispersing agent and preparation method thereof |
| CN116282600A (en) * | 2023-04-17 | 2023-06-23 | 扬州颖浩环保科技有限公司 | High-salt wastewater salt-resistance dispersing agent |
| CN116282600B (en) * | 2023-04-17 | 2024-01-09 | 扬州颖浩环保科技有限公司 | High-salt wastewater salt-resistance dispersing agent |
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