CN1807287A - Highly effective multifunctional reverse osmosis membrane antiscaling agent and its preparation method - Google Patents

Abstract

The invention discloses a high performance multifunctional reverse osmosis membrane antisludging agent and process for preparation, wherein the constituents include ether-containing hypophosphorous acid, P-containing polymer, dispersing agent, bactericidal agent and purified water.

Description

A kind of highly effective multifunctional reverse osmosis membrane antiscaling agent and preparation method thereof

One, technical field:

The present invention relates to a kind of medicament for water treatment with reverse osmosis membrane highly effective multifunctional reverse osmosis membrane antiscaling agent and preparation method thereof, do not find the patented technology identical by retrieval with the present invention.

Two, background technology:

Along with the continuous expansion of Chinese Urbanization, industrial degree deepens constantly.Adopting underground water to do service water has certain restriction again, so modern heat power plant boiler water major part will be considered to handle use with surface water.In order to guarantee the quality of boiler feed water, modern thermal power generation corporations extensively adopt reverse osmosis technology, set up thermal power plant's water treatment system.A large amount of dirt precipitations can appear in the reverse osmosis equipment long-time running, cause dirty stifled phenomenon.Dirty stifled appearance, directly cause a large amount of energy consumptions and frequent cleaning, the reverse osmosis effect descends, and serious will change the most valuable membrane element at short notice, the water treatment comprehensive cost is raise, therefore the research of the dirty cause of blocking up of reverse osmosis is also day by day goed deep into.The pollution of reverse-osmosis membrane element can be divided into particle contamination, microbial contamination, inorganic salt chemical pollution and colloid pollution, for particle contamination, can adopt suitable flocculation agent and filtering system to solve.For biological pollution, can adopt suitable sterilant, germicidal lamp or other system to solve.For inorganic scale and colloid fouling, then adopt the method that adds efficient scale inhibitor to solve.The formation of inorganic scale be since the concentration of the inorganic salt of film surface dissolution increase cause.If the ionic product of dissolved salt will produce precipitation during greater than its solubility product, cause the film surface scale, exemplary such as lime carbonate, magnesiumcarbonate, calcium sulfate, sal epsom and the Calcium Fluoride (Fluorspan) of deposition salt.And the major cause that forms the colloid dirt is iron, aluminium and silicon.

Abroad, with reverse osmosis system carry out that the research of water treatment carries out early, also comparative maturity aspect the maintenance technology of reverse osmosis system been has has been researched and developed serial novel reverse osmosis antisludging agent in succession.Because China does not still have the enterprise of a tame professional production reverse osmosis antisludging agent so far, except enterprise seldom also using common Sodium hexametaphosphate 99, needed efficient reverse osmosis antisludging agent all is from external import more than 90%.Over past ten years, external and domestic reverse osmosis system company has built hundreds of cover reverse osmosis systems in China and has been used for water treatment, and these systems more or less all need to adopt reverse osmosis antisludging agent to safeguard, so China's reverse osmosis antisludging agent market outlook are very wide., by the end of the year 2002, the whole nation to the demand of reverse osmosis antisludging agent reference liquid more than 3000 tons.Generally speaking, the average price of reverse osmosis antisludging agent reference liquid per ton is at 6.0 ten thousand yuans, so the market value of the annual reverse osmosis antisludging agent of China is at 200,000,000 yuans.The demand of this medicament will be bigger from now on, and it is considerable to produce this medicament benefit.

I have developed the scale inhibition series product that are used for reverse osmosis system on the basis of the external imported product of long-term follow.Can both provide relevant treatment formulations requirement at domestic various water quality.On probation through domestic many enterprises, prove that the reverse osmosis scale inhibition effect can compare favourably with external imported product fully, some index even surpass external product, and also product performance stablize, and price is but well below external product.

Three, summary of the invention:

The invention solves the situation of reverse osmosis membrane antisludging agent dependence on import, some domestic small business causes reverse osmosis membrane self-adhesion connection because of the domestic reverse osmosis membrane antisludging agent of the immature use of technology, and dirty stifled phenomenon film is scrapped.Product of the present invention not only has the high-performance scale effect, and the also good germicidal action of tool to microbial contamination, can effectively be controlled.

Technical scheme of the present invention is as follows:

In order to realize the above-mentioned purpose of product of the present invention, a kind of highly effective multifunctional reverse osmosis membrane antiscaling agent that product of the present invention provided comprises being selected from hereinafter to be referred as ROMDC150 and contains ether phosphoric acid, phosphorous polymer, dispersant with high efficiency, sterilant and water.Be mixed in proportion and add above-mentioned raw materials and water successively and be heated to 20 ℃ of 60 ℃ of insulations coolings in 1-3 hours.Add sterilant and stirred 0.5 hour, static, filter, check, packing, warehouse-in.All percentage ratios of following effective constituent and content are weight percentage.

Contain ether phosphoric acid: 10-40%

Phosphorous polymer: 10-30%

Dispersant with high efficiency: 5-20%

Sterilant: 5-15%

Water: an amount of

The described ether phosphoric acid that contains is selected from polyamino polyether methylene phosphoric acid PAPEMP.

Described phosphorous polymer is selected from multi-functional sulfonic phosphoryl carboxylic acid copolymer p OCA, PAA-AMPS-HPA terpolymer, one or more of 2-phosphate butane 1,2,4 tricarboxylic acid PBTCA.Described dispersant with high efficiency is selected from the hydrolytic polymaleic anhydride HPMA of molecular weight about 800.Described sterilant is selected from 2.2 2 bromo-2-nitroethyl alcohols, one or more of 1.2-2-nitro-1.3-propylene glycol.Described water is pure water.

Four, embodiment, the invention will be further described below in conjunction with embodiment.

Embodiment 1:

Choose raw material by weight percentage

Contain ether phosphoric acid PAPEMP 10-40%

Phosphorous polymer PBTCA 10-30%

Dispersant with high efficiency HPMA 5-20%

Sterilant 1.2-2-nitro-1.3-propylene glycol 5-15%

Pure water is an amount of

Above-mentioned raw materials is mixed in proportion add PAPEMP, PBTCA, HPMA successively, pure water is heated to 60 ℃ of insulations 1-3 hour, cools to 20 ℃, adds 1.2-2-nitro-1.3-propylene glycol at last, stirs 0.5 hour, and is static, filter, check, packing, put in storage.

Embodiment 2,

The reverse osmosis antisludging agent kind is more in the market, and product performance differ greatly.We have carried out resistance lime carbonate, calcium sulfate, dispersing iron oxide and flocculation agent compatibility to the PTP0100 of the HYPERSPERSE MDC200 of representative BetzDearbobn (Bei Di) company and MDC150 Scale inhibitors, KINGLEE (clear power) company and PTP2000 Scale inhibitors and product RO MDC150 of the present invention series Scale inhibitors and have compared.

Two, test and result

1. test sample is originated

See Table 1

Table 1 test sample source

Business Name	The medicament title
		Product of the present invention	RO MDC150
Bei Di company	HYPERSPERSE MDC200
		HYPERSPERSE MDC150
	Clear power company		PTP 0100
PTP 2000

2. hinder CaCO ₃Test

2.1 experimental water: water distribution: Ca ²⁺280mg/L; HCO ₃ ^-732mg/L.

2.2 test conditions:

Water temperature: 50 ℃

Time: 20 hours

Dosing: 5mg/L

2.3 experimental technique:

See GB16632-1996

2.4 experimental result: see Table 2

Table 2 CaCO ₃Scale inhibition performance

Business Name	The medicament title	Scale inhibition performance %
			Product of the present invention	RO MDC150	100
Bei Di company	HYPERSPERSE MDC200	60.5
			HYPERSPERSE MDC150	80.7
	Clear power company	PTP 0100			95.45
PTP 2000			55.94

3. hinder CaSO ₄Test

3.1 experimental water: water distribution: Ca ²⁺6500mg/L; SO ₄ ^2-6900mg/L.

3.2 test conditions

Water temperature: 50 ℃

Time: 20 hours

Dosing: 5mg/L

3.3 experimental result: see Table 3

Table 3 CaSO ₄Scale inhibition performance

Business Name	The medicament title	Scale inhibition performance %
			Product of the present invention	RO MDC150	99.88
Bei Di company	HYPERSPERSE MDC200	70.26
			HYPERSPERSE MDC150	86.20
	Clear power company	PTP 0100			56.69
PTP 2000			97.83

4. dispersing iron oxide performance test

4.1 test method

Preparation Ca ²⁺150mg/L is (with CaCO ₃Meter) 5mg/L Scale inhibitors and 10mg/LFe ²⁺Aqueous solution 500mL places the 1000mL beaker, regulates pH value with the 0.5g/L sodium tetraborate while stirring.When pH value reach 8.77 and stable after, violent stirring 15 minutes left standstill 5 hours in 50 ℃ of water-baths then, got supernatant liquid, surveyed transmittance with spectrophotometer (420nm).

4.2 experimental result

See Table 4

Table 4 Fe ₂O ₃Dispersed

Business Name	The medicament title	Transmittance %
			Product of the present invention	RO MDC150	80.1
Bei Di company	HYPERSPERSE MDC200	84.6
			HYPERSPERSE MDC150	84.3
	Clear power company	PTP 0100			85.0
PTP 2000			83.0

Transmittance is more little, shows that the medicament dispersing property is good more.By table as seen, several prods dispersing iron oxide performance is suitable.

5. with the flocculation agent compatibility test

The compatibility test of several medicaments and flocculant poly aluminum chloride, cationic polyacrylamide and the flocculation agent MPT150 of Bei Di company sees Table 5

Table 5 compatibility test

Business Name	The medicament title	Flocculation agent
					PAC	Cationic PAM	Shellfish enlightening MPT150
		Product of the present invention	RO MDC150	-				-	-
Bei Di company	HYPERSPERSE MDC200				+	+	+
		HYPERSPERSE MDC150	+	-				-
	Clear power company				PTP 0100	-	-		-
PTP 2000		+	-	-

Annotate: "-" expression is compatible, "+' represent incompatible

As seen, the PTP0100 of the RO MDC150 of product of the present invention, clear power company and flocculation agent are compatible entirely; The PTP2000 of clear power company, the MDC150 of Bei Di company and MDC200 and inorganic flocculating agent PAC are incompatible.MDC200 with the flocculation agent that tries all incompatible, MDC150 only with the organic floculant compatibility.Therefore, whether when selecting Scale inhibitors, it is compatible at first will to investigate medicament and flocculation agent, if incompatible, just easily cause the obstruction of reverse osmosis membrane, and can't clean, and equipment is scrapped very soon.

Embodiment 3,

The 60MW that now installs of Xinjiang electricity generating corporation, Ltd has a cover 60M ³The reverse osmosis system that/h exerts oneself is used for the boiler of power plant supplementary feed.Use product reverse osmosis antisludging agent RO MDC150 of the present invention so far from June, 2003, equipment operational excellence, system are moved every index and are all reached design requirements, and pressure reduction is stable not to rise, and fresh water is exerted oneself and is stabilized in 60M ³/ h.RO MDC150 is cheap, and is easy to use, and great advantage is exactly that scale inhibition is good, need not use pretreating agent PAC reaction, good with the flocculation agent compatibility.System operation so far, under the situation of adding of germicide not, aseptic algae produces, and has guaranteed the safety and economic operation of power plant.

Five, conclusion

To sum up analyze, from resistance CaCO ₃Dirt, CaSO ₄Compatible these several salient featuress of dirt, dispersing iron oxide and flocculation agent more as can be known, the RO MD150 practical application effect of product of the present invention reaches the level of international advanced product fully, on part index number, also be better than foreign brand name, and homemade scale remover has superiority on the price.Along with the requirement that China's scientific technological advance and enterprise constantly reduce cost, it is a kind of inexorable trend that homemade Scale inhibitors finally will replace the external import Scale inhibitors that captures the domestic market at present.

Claims (2)

1, a kind of highly effective multifunctional reverse osmosis membrane antiscaling agent and preparation method thereof is characterized in that and will contain ether phosphoric acid, phosphorous polymer, dispersant with high efficiency, sterilant and water, wherein each compositions in weight percentage:

Contain ether phosphoric acid 10-40%

Phosphorous polymer 10-30%

Dispersant with high efficiency 5-20%

Sterilant 5-15%

Water is an amount of

Above-mentioned raw materials is mixed in proportion successively adds that to contain ether phosphoric acid, phosphorous polymer, dispersant with high efficiency, water an amount of.Be heated to 60 ℃ of insulations 1-3 hour, cool to 20 ℃, add sterilant at last, stirred 0.5 hour, filter, check, pack, put in storage.

2, the ether phosphoric acid that contains according to claim 1 is selected from polyamino polyether methylene phosphoric acid PAPEMP; Contain the phosphine polymkeric substance and be selected from multi-functional sulfonic phosphate polymers of carboxylic acid POCA, one or more of 2-phosphate butane 1.2.4 tricarboxylic acid PBTCA; Dispersant with high efficiency is selected from the hydrolytic polymaleic anhydride HPMA of molecular weight about 800; Sterilant is selected from 2.2 2 bromo-2-nitroethyl alcohols, one or more of 2-bromo-2-nitro-1.3-propylene glycol; Described water is pure water.