PAPEMP

Polyamino Polyether Methylene Phosphonic Acid  = PAPEMP

CAS Number : 130668–24–5
EC / List no.: 682-650-0
Density (20℃)g/cm3: 1.20±0.05

PAPEMP also effectively restrain the Si scale from a formation and stabilize the ions. Such as Mn, and Fe to form chelating compounds.
PAPEMP also has a good tolerance to high temperature, high turbidity, high salt concentration, and high chlorine (Cl– and Br–) concentration. 
PAPEMP  can be used as scale and corrosion inhibitor in circulating cool water system and oilfield refill water system in situations of high hardness, high alkali, and high pH value.
PAPEMP can be used as a scale inhibitor for a reverse osmosis system and a multistep flash vaporization system.

PAPEMP can significantly inhibit calcium carbonate precipitation from the aqueous solution by modifying the crystal morphology
PAPEMP is a new kind of water treatment agent. 
PAPEMP has high chelation and dispersion effects, high value of calcium tolerance, and good scale inhibition effects. 
PAPEMP can be used as scale and corrosion inhibitor in circulating cool water system and oilfield refill water system in situations of high hardness, high alkali and high pH value. 


PAPEMP has excellent scale inhibition ability to calcium carbonate, calcium sulfate and calcium phosphate. 
PAPEMP can efficiently inhibit the formation of silica scale, stabilize metal ions such as Zn, Mn and Fe.
PAPEMP can be used as scale inhibitor for reverse osmosis system and multistep flash vaporization system in which high salt concentration, high turbidity and high temperature are usually encountered (such as high temperature and high turbidity in coal vaporization system), accessory agent for woven & dyeing (for example, yellow turnback inhibition agent), as alternatives of EDTA, DTPA and NTA.
Usage of PAPEMP :The good adaption to different situations enables PAPEMP widely used in boiler, cooling water system and oilfield reinjection water as antiscalant and corrosion inhibitor.


PAPEMP is a new kind of scale inhibitor for industrial water treatment. 
PAPEMP has high chelation and dispersion effect with high value of calcium tolerance and scale inhibition effect. 
PAPEMP can be used as scale and corrosion inhibitor in circulating cooling water system and oilfield of high hardness including calcium magnesium and barium sulfate scale inhibitor. 

PAPEMP is stable in aqueous solution under a wide range of pH, temperature and pressure.
Polyamino polyether methylene phosphonate widens the operational conditions available with today’s standard technology by allowing operations with hard water at higher pH levels and greater salt concentrations. 
PAPEMP it is possible to operate at up to 300X calcite saturation because of its excellent calcium tolerance. 
As a result it controls up to three times as much calcium carbonate as ATMP or PBTC (operating at up to 100x calcite saturation).


Polyamino Polyether Methylene Phosphonate
Molecular weight: about 600
PAPEMP Acid- Polyamino polyether methylene phosphonic acid
Structural Formula:
CH2(OCH2CH)nCH3NCH2CH2P(OH)2P(OH)2OOHCCH3NCH2CH2(HO)2P(HO)2POO


PAPEMP (Polyamino Polyether Methylene Phosphonate) Properties:
PAPEMP performs excellently in the condition of high hardness and pH as a new antiscalant and corrosion inhibitor. 
With high calcium tolerance, PAPEMP scale inhibition ability is also high, particularly for CaCO3, CaPO4, and CaSO4.


Polyamino polyether methylene phosphonate (PAPEMP) is very effective in preventing calcium carbonate precipitation at high supersaturation and high pH. 
The inhibition of calcium carbonate crystallization in the presence of PAPEMP at both low and high supersaturation was studied and then compared to the inhibitory ability of hydroxyethylidene-1 ,1-diphosphonic acid (HEDP). 
Keywords: calcium carbonate inhibition, crystallization kinetics, phosphonates, affinity constants, calcium tolerance.


PAPEMP is a new kind of water treatment agent. 
PAPEMP has high chelation and dispersion effects, high value of calcium tolerance, and good scale inhibition effects.  
PAPEMP is as scale and corrosion inhibitor in circulating cool water system and oilfield refill water system in situations of high hardness, high alkali and high pH value.  
PAPEMP inhibits scale formation of calcium carbonate, calcium sulfate and calcium phosphate.  


Polyamino Polyether Methylene Phosphonic Acid is a new kind of water treatment agent. 
PAPEMP has high chelation and dispersion effects, high value of calcium tolerance, and good scale inhibition effects. 
Polyamino Polyether Methylene Phosphonic Acid can be used as scale and corrosion inhibitor in circulating cool water system and oilfield refill water system in situations of high hardness, high alkali and high pH value. 

Polyamino Polyether Methylene Phosphonic Acid has excellent scale inhibition ability to calcium carbonate, calcium sulfate and calcium phosphate. 
Polyamino Polyether Methylene Phosphonic Acid can efficiently inhibit the formation of silica scale, stabilize metal ions such as Zn, Mn and Fe.
Polyamino Polyether Methylene Phosphonic Acid can be used as scale inhibitor for reverse osmosis system and multistep flash vaporization system in which high salt concentration, high turbidity and high temperature are usually encountered (such as high temperature and high turbidity in coal vaporization system), accessory agent for woven & dyeing (for example, yellow turnback inhibition agent), as alternatives of EDTA, DTPA and NTA.


Applications of PAPEMP:
· PAPEMP has excellent scale inhibition ability to calcium carbonate, calcium sulfate and calcium phosphate.
· PAPEMP can efficiently inhibit the formation of silica scale,stabilize metal ions such as Zn, Mn and Fe. It effectively chelates metal ions including calcium, magnesium, iron and copper.
· PAPEMP can be used as scale inhibitor for reverse osmosis system and multi-step flash vaporization system in which high salt concentration, high turbidity and high temperature are usually encountered (such as high temperature and high turbidity in coal vaporization system), accessory agent for woven & dyeing (for example, yellow turn back inhibition agent), as alternatives of EDTA, DTPA and NTA .


Synonyms:
· PAPEMP
· Polyoxypropylenediaminetetramethylenephosphonic acid


CAS No. : 130668–24–5

Product Use : Scale and corrosion inhibitor intermediate
Chemical Name : Polyamino Polyether Methylene Phosphonic Acid


Appearance: Amber transparent liquid
Solid content %: 45.0min
Active component (PAPEMP) %: 40.0min
Phosphoric acid (as PO43-)%: 1.0max
Density (20℃)g/cm3: 1.20±0.05
pH(1% solution): 2.0±0.5

PAPEMP usage:
The dosage of 5-100mg/L is preferred. Different from other water treatment agents, the more quantity is, the better the effect. 
PAPEMP can be used with polycarboxylic acids.

PAPEMP Package and Storage:
Normally In 250kg net Plastic Drum, IBC drum can also be used as required. Storage for ten months in room shady and dry place.


The new calcium carbonate inhibitor is PolyAmino PolyEther Methylene Phosphonate (PAPEMP). 
One of the particular advantages of the PAPEMP molecule is its exceptional calcium tolerance. 
Calcium tolerance is a measure of a chemical compound’s ability to remain soluble in the presence of calcium ions (Ca2+) under both high pH and high temperature, such as in geothermal brines. 
As pH and temperature increases, calcium tolerance decreases rapidly for traditional CaCO3 threshold inhibitors, e.g., 1-hydroxy ethylidene 1,1-diphosphonic acid (HEDP), amino tri (methylene phosphonic acid) (AMP), and polyacrylic acid. 

The X-axis in this figure is the amount of HEDP as PPM needed to form precipitation in a water containing 10,000 PPM of Calcium ions. 
The data for temperature curve was collected at pH 9, while the pH curve represents data at 250°F. 
At higher temperature and/or higher pH, it requires


Poly amino polyether methylene phosphonate (PAPEMP) is a very effective inhibitor in preventing CaCO3 precipitation. 
The extraordinary affinity of PAPEMP towards CaCO3 surfaces and its excellent tolerance of calcium materials make this polymer excellent in inhibiting the growth of CaCO3 crystal. 
Amjad et al. have extensively studied phosphonate-based polymer performance in cold water. 
They have studied the effectiveness of phosphate and phosphonate polymers in stabilized and all-organic cooling water treatment facilities. 
This study reported that these polymers are capable of performing a dual function. 

Firstly, they control the thickness of the calcium phosphate and phosphonate membrane on the metal surface. 
Secondly, they prevent the precipitation of the calcium phosphate and phosphonate salts in the recirculating water. 
Another study conducted by the same research group demonstrated the performance of sulphonic-acid-containing terpolymer for controlling the growth of calcium phosphonates and carbonate scale. It showed that these polymers improved the control of calcium phosphonate and carbonate in highly stressed cooling water systems [28]. 
Wang et al. also conducted a similar study in which they have reported the inhibition of CaCO3 by a phosphonate-terminated poly(maleic-co-sulfonate) polymeric inhibitor. 
This study showed that this inhibitor is capable of controlling CaCO3 scale 

Polyamino Polyether Methylene Phosphonate (PAPEMP)
Investigation of CaCO3 scale inhibition by PAA, ATMP and PAPEMP
Calcium carbonate scale inhibition by three inhibitors, polyacrylic acid (PAA), aminotrimethylenephosphonic acid (ATMP) and polyamino polyether methylenephosphonate (PAPEMP), has been investigated by the bubbling method, and the calcium carbonate scales formed in the absence and presence of inhibitors have been examined by SEM and XRD. 
It was found that ATMP shows “threshold effect” in the inhibition of CaCO3 scale, and the inhibition behavior of PAPEMP is similar to that of PAA: the “threshold effect” is not observed. 
In the presence of inhibitors, the normal growth of calcium carbonate is disturbed, and in the presence of PAPEMP, the scale morphology is similar to that in the presence of ATMP. The vaterite phase is effectively stabilized kinetically in the presence of PAA; ATMP takes second place, and PAPEMP can hardly stabilize kinetically the vaterite phase

In recent years, the percentage of oil production from more challenging environments has increased. 
In addition to the numerous engineering and logistical difficulties of working at increased depth, temperature and pressure these production zones provide a harsh environment deleterious to the performance of some critical oilfield chemicals. 
Scale inhibitors are one class of oil field chemicals which are deployed through squeeze treatments into the formation and/or continuous downhole injection for protection of production tubulars. 
As well depths continue to increase, the exposure time of the injected chemicals also increases. 
With temperatures in the range of 180-200 °C and pressures exceeding 10,000 psi, the effect of elevated temperature and pressure on scale inhibitor performance is a critical parameter to evaluate using chemical analytical techniques and product performance methods.

Another trend leading to increased thermal exposure is the use of thermal enhanced recovery techniques. 
Scale inhibitors are exposed to high temperatures in operations such as steam flooding and steam assisted gravity drainage (SAGD).
In this study, a range of chemicals have been evaluated for their short and medium-term thermal stability at 180 and 200 °C. 
The primary application of this data is for downhole injection and squeeze treatments prior to adsorption. 
Inhibitor chemical types include sulfonated polycarboxylic acid (SPCA), fluorescent tagged sulfonated polycarboxylic acid (FSPCA), phosphorous tagged sulfonated polycarboxylic acid (PSPCA), sulfonated polyacrylocarboxylic acid (SPAC), polyacrylic acid (PAA), polyvinyl sulfonate (PVS), polyamino polyether methylene phosphonate (PAPEMP), bis(hexamethylene)triamine pentakis(methylene phosphonic acid) (BHTPMP) and diethylenetriamine pentakis(methylene phosphonic acid) (DTPMP). 

In most cases the sodium or potassium salts of the inhibitors are used.
The chemical effect of temperature on scale inhibitors is measured through molecular weight determination, thermogravimetric analysis (TGA), pH change, and Fourier Transform Infrared (FTIR) analysis. 
The performance of these inhibitors is measured under static and dynamic conditions for inhibition of barium sulfate scale. 
These results help to further the knowledge of inhibitor degradation due to thermal effects and indicate the direction for further product development of thermally stable scale inhibitors.


Walsh University, Division of Mathematics and Sciences, North Canton OH 44720, USA
Abstract: The effects of poly(acrylic acid), PAA, polyamino polyether methylene phosphonic acid, PAPEMP, and PAA/PAPEMP blend on calcium sulfate dihydrate (gypsum) are reported in this paper. 
PAPEMP has been found that gypsum inhibition by PAA increases with increasing PAA concentration. 

Among the various phoshonates (i.e., aminotris(methylene phosphonic acid), AMP; hydroxyphosphono acetic acid, HPA; hydroxyethylidene 1,1-diphosphonic acid, HEDP; 2-phosphonobutane 1,2,4-tricarboxylic acid, PBTC; and polyether polyamino phosphonic acid, PAPEP) evaluated, PAPEMP shows the best inhibition for gypsum precipitation. 
PAPEMP has also been observed that presence of PAPEMP exhibits synergistic effect on the performance of PAA. 
Results on calcium ion compatibility of various phosphonates show that PAPEMP compared to other phosphonates tested show higher tolerance to calcium ions.
Keywords: calcium sulfate dihydrate, precipitation, inhibition, polymer, phosphonates

PAPEMP properties :
PAPE is a new kind of water treatment chemicals. 
PAPE has good scale and corrosion inhibition ability. 
Because more than one ployethylene glycol group is introduced into the molecular, the scale and corrosion inhibition for calcium scale is improved. 
PAPE has good inhibition effect for barium and strontium scales. 
PAPE has good scale inhibition effect for calcium carbonate and calcium sulfate, it can mix well with polycarboxylic acid, organophoronic acid, phosphate and zinc salt.
PAPE can be used as scale inhibitor for oilfield (recommended as alternatives of Nalco Visco 953) and industrial cool water system.


Deposition of unwanted materials, including mineral scales, suspended matter, microbiological growth, and corrosion products, continues to plague the operation of industrial water systems. 
This article presents performance data on polyamino polyether methylene phosphonic acid (PAPEMP) on various mineral scales commonly encountered in boiler, cooling, desalination, geothermal, gas, and oil systems.
Water that is available for domestic and industrial applications typically contains many impurities. 

These impurities are generally classified in five broad categories:
• Dissolved inorganic compounds (i.e., carbonates, sulfates, phosphates, and fluorides of calcium, magnesium, barium, and strontium; small amounts of copper [Cu], iron [Fe], and manganese [Mn]); and other substances
• Dissolved gases (e.g., oxygen [O2], nitrogen [N2], carbon dioxide [CO2], and hydrogen sulfide [H2S])
• Suspended matter (e.g., clay, silt, fat, and oil)
• Soluble organic compounds (e.g., humic acid, fulvic acid, and tannic acid)
• Microorganisms (e.g., algae, bacteria, and fungi)

The accumulation of unwanted deposits on equipment surfaces is a phenomenon that occurs in virtually all processes in which untreated water is heated. 
The deposition of these materials, especially on heat exchanger surfaces in boiler, cooling, geothermal, and distillation systems, can cause a number of operational problems such as plugged pipes and pumps, inefficient use of water treatment chemicals, increased operational costs, lost production due to system downtime, and ultimately heat exchanger failure.
Greater water conservation has been a driver for operating industrial water systems at higher concentration cycles, which increases the potential for deposit buildup on heat exchanger surfaces. 

Operating industrial water systems under stressed conditions demands a better understanding of the feed and recirculating systems’ water chemistry as well as the development of innovative additives and technological approaches for controlling scale, deposit, corrosion, and biofouling.
The most promising scale control method among various approaches involves adding substoichiometric dosages, typically a few ppm, of water-soluble additives to the feedwater. 
Additives commonly used in water treatment formulation fall into two categories:

• Dissolved inorganic compounds (i.e., carbonates, sulfates, phosphates, and fluorides of calcium, magnesium, barium, and strontium; small amounts of copper [Cu], iron [Fe], and manganese [Mn] ions; and other substances)
• Polymeric (e.g., homopolymers of acrylic acid, maleic acid, itaconic acid, aspartic acid, and copolymers containing monomers of different functional groups)
Although there are many phosphonates available, three of the most commonly used phosphonates in water treatment formulations are aminotrismethylene phosphonic acid (AMP); 1-hydroxyethylidine, 1,-1 diphosphonic acid (HEDP); and 2-phosphono-butane 1,2,4-tricarboxylic acid (PBTC). 
However, under certain pH, concentration, and temperature conditions, phosphonates have been shown to precipitate in the presence of calcium ions. 
The precipitation of calcium phosphonate salts not only creates fouling of heat exchanger and reverse osmosis (RO) membrane surfaces, it also decreases the solution concentration of a phosphonate to such an extent that severe calcium carbonate (CaCO3) scaling can occur. 
The focus of this study is to evaluate the performance of polyamino polyether methylene phosphonic acid (PAPEMP) as an inhibitor for various scales (e.g., CaCO3, calcium sulfate dihydrate [CaSO4•2H2O], and calcium phosphate [Ca3(PO4)2]) and a stabilization agent for Fe(III) or Fe3+ ions.

Experimental Protocols
All chemicals were obtained from commercial sources. 
They include AMP, HEDP, PBTC, 2-hydroxyphosphono acetic acid (HPA), PAPEMP, and polyacrylic acid (PAA). 
Detailed procedures for reagents solution preparation; percent inhibition (%I) calculation for calcium sulfate dihydrate (CaSO4•2H2O), CaCO3, Ca3(PO4)2, and Fe3+ stabilization; and instruments used are reported elsewhere.3-6 Table 1 lists the inhibitors tested.


PAPEMP production process consists of 4 steps.
Phosphorus acid is input into the reactor and its pH is adjusted by HCl.
Polyetheramine is instilled and the reaction starts while the reactor is heated.
Formaldehyde is input a few hours later.
The reactor will be further heated and steamed for more hours.


For the same reason, PAPEMP is also applied in RO and multistep flash system. 
Recommend dosage is 5-100 ml/L. Unlike other organophosphonates, there is no optimum dosage for it. 
Higher the dosage, better the effect.

Besides, PAPEMP works as a nutrient absorber in agriculture. 
PAPEMP can also replace those more expensive color transfer inhibitors (eg. yellow turnback inhibitor) like EDTA, NTA, and DTPA in textile dyeing.

Calcium carbonate scale inhibition by three inhibitors, polyacrylic acid (PAA), aminotrimethylenephosphonic acid (ATMP) and polyamino polyether methylenephosphonate (PAPEMP), has been investigated by the bubbling method, and the calcium carbonate scales formed in the absence and presence of inhibitors have been examined by SEM and XRD. 
It was found that ATMP shows “threshold effect” in the inhibition of CaCO3 scale, and the inhibition behavior of PAPEMP is similar to that of PAA: the “threshold effect” is not observed. 
In the presence of inhibitors, the normal growth of calcium carbonate is disturbed, and in the presence of PAPEMP, the scale morphology is similar to that in the presence of ATMP. 
The vaterite phase is effectively stabilized kinetically in the presence of PAA; ATMP takes second place, and PAPEMP can hardly stabilize kinetically the vaterite phase.
Poly-amino poly-ether methylenephosphonic acid (PAPEMP)-containing corrosion and scale inhibitor

Abstract
The invention provides a poly-amino poly-ether methylenephosphonic acid (PAPEMP)-containing corrosion and scale inhibitor, belongs to the technical field of water treatment and relates to a corrosion and scale inhibitor. 
The corrosion and scale inhibitor comprises PAPEMP, a zinc salt, a dispersant, a copper corrosion inhibitor and water. 
The corrosion and scale inhibitor has a reasonable formula, has good use effects and a low production cost, is suitable for an open circulated cooling water system and is especially suitable for a high-hardness, high-basicity and high-pH circulated cooling water system.

PAPEMP is excellent to the scale-inhibiting properties of calcium carbonate, calcium phosphate, calcium sulfate, effectively can suppresses the formation of silicon dirt simultaneously, and there is the effect of satisfactory stability metal ion as zinc, manganese, iron.
PAPEMP is a new kind of water treatment agent. XF-335S (PAPEMP) has high chelation and dispersion effects, high value of calcium tolerance, and good scale inhibition effects.
PAPEMP can be used as scale and corrosion inhibitor in circulating cool water system and oilfield refill water system in situations of high hardness, high alkali and high pH value. 

PAPEMP has excellent scale inhibition ability to calcium carbonate, calcium sulfate and calcium phosphate. 
PAPEMP can efficiently inhibit the formation of silica scale, stabilize metal ions such as Zn, Mn and Fe.
PAPEMP can be used as scale inhibitor for reverse osmosis system and multistepflash vaporization system in which high salt concentration, high turbidity and high temperature are usually encountered (such as high temperature and high turbidity in coal vaporization system), accessory agent for woven & dyeing, as alternatives of EDTA, DTPA and NTA . 

Poly[oxy(methyl-1,2-ethanediyl)], a-[2-[bis(phosphonomethyl)amino]methylethyl]-w-[2-[bis(phosphonomethyl)amino]methylethoxy]-
POLYAMINO POLYETHER METHYLENE PHOSPHONIC ACID
130668-24-5

Calcium carbonate has been identified as the main problem associated with industrial cooling water scaling or deposition. 
The formation of calcium carbonate scale in industrial cooling water system has been known to pose significant problems to the industrial processes. 
The calcium carbonate scales or deposits will serve as a heat insulating layer that reduces heat transfer efficiency and hence require higher energy consumption to attain the desired cooling or heating effect (Prisciandaro et al., 2013). 
Therefore, PAPEMP is vital to ensure that heat transfer surfaces on industrial cooling water systems are relatively free from calcium carbonate scaling problems. 

Most of the research works on crystal growth inhibition of industrial cooling water treatment program were conducted by a few multinational water treatment companies at their own research center. 
This valuable information is unfortunately not available to others due to trade secret. 
As such smaller water treatment companies that have limited resources have limited information in developing the right formulation in their cooling water treatment program. 
This study aims to provide such information so that it can be made available to enhance the technical competency of calcium carbonate scale inhibition. 


Calcium carbonate crystal growth inhibition by the simplest form of phosphate-containing compounds, orthophosphate, has been well studied by several researchers and orthophosphate concentration in the range of several milligrams per liter have been found to retard the crystal growth in seeded solutions. 
Adsorption of orthophosphate on calcium carbonate scale has been studied and found to change the structure of calcium carbonate crystal lattice. 
In another study, CaHPO4 was found to be the responsible species that absorbs on the calcium carbonate surface and inhibits further precipitation. 
The use of polyphosphates for calcium carbonate crystal growth inhibition was also investigated and sodium tri-polyphosphate was found to be the strongest inhibitor in a mono polyphosphate formulation followed by sodium pyrophosphate and sodium hexametaphosphate. 

However, orthophosphate and polyphosphates were excluded in this study, driven by market trend towards low or non-phosphorus compounds used for such application in consideration of environmental issues such as eutrophication associated with phosphorus compounds. 
Calcium carbonate scale inhibition by organophosphorus compounds such as amino tris(methylene phosphonic acid) (ATMP), ethylene-diamine tetra(methylenephosphonic acid) (EDTMP), hexamethylenediamine tetra(methylenephosphonic acid) (HDTMP), diethylenetriamine penta(methylenephosphonic acid) (DTPMP) and PAPEMP were also being investigated. 
Results shown that the phosphonic group number and the methylene chain length play a vital role in the effectiveness of the inhibitors. 


Although the application of most organophosphorus compound contributes lesser phosphorus to the environment in relative term to orthophosphate and polyphosphates, some of the commonly used compounds such as ATMP still contains considerable amount of phosphorus (31 % as Phosphorus) and 1-hydroxyethane 1,1-diphosphonic acid (HEDP) (30 % as Phosphorus). 
Owing to the environmental consideration, this study has selected non-phosphorous polymeric compound represented by PMA and AA/MA copolymer and low phosphorus contributor PAPEMP (about 20 % as Phosphorus) for the tests. 
The inhibition of calcium carbonate crystal growth by PMA, PAPEMP and AA/MA copolymer was investigated via static beaker tests at typical water chemistries encountered in cooling water system. 
his study provides a method that enables the evaluation of scale inhibitors at the practical dosage level and economically viable range at various water chemistries encountered in the market place, thus providing a practical and useful solution and background formulation information to water treatment professionals to mitigate industrial cooling water scaling and deposition problems for a given water chemistries and condition. 
The desired inhibition efficiency of minimum 90 % was set up to evaluate and compare the performance of the above inhibitors.

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