The method of obtaining inhibitor deposits of mineral salts

 

(57) Abstract:

The invention relates to a method for inhibiting deposits of mineral salts by the interaction of derivatives of ammonia, including ammonium chloride or waste production polyethylenepolyamines, with formaldehyde and phosphorous acid as such or a product of hydrolysis of phosphorus trichloride in an environment of diluted hydrochloric acid at elevated temperature, followed by neutralization of the resulting solution with sodium hydroxide to pH 6,51,0, and the process is conducted at a molar ratio of the initial reagents ammonia: formaldehyde: phosphoric acid 1,0:2,35-2,65:2,2-2,4. The resulting inhibitor deposits of mineral salts is highly effective at stabilizing treatment of water with carbonate index of 15 (mEq/l)2and the outlet water temperature of the water boiler 110-140oC. table 3.

The invention relates to the chemistry of phosphorus-containing compounds, namely to obtain aminophosphonates used as inhibitors of deposits of mineral salts for the stabilization of water treatment systems, water supply enterprises of metallurgical, chemical, petrochemical and other field the receipt of such inhibitors interaction of derivatives of ammonia /hexamethylenetetramine or ammonium chloride/ (SU 960184, 1982, SU 992519, 1983) or aliphatic polyamines /ethylene diamine, diamine/ (SU 703545, 1979) with formaldehyde and phosphorous acid is the product of the hydrolysis of phosphorus trichloride or saponification VAT residue production dimethylphosphite.

As a prototype and the underlying object taken by the method described in (SU 1362735, 1987). Inhibitor of deposits of mineral salts by this method is obtained by interaction of ammonium chloride /including waste production polyethylenepolyamines/ with formaldehyde and phosphorous acid in the presence of hydrochloric acid; to obtain phosphorous acid hydrolyzing phosphorus trichloride, fending off the water hydrogen chloride. The process of methyltestosterone carried out at a molar ratio of reagents ammonium chloride : formaldehyde : phosphoric acid of 1.0:1.8-to 2.2 1.8 to about 2.2, respectively.

Thus obtained, the inhibitor is effectively used in the following conditions: water temperature at the outlet of the hot water boiler is not more than 110oC, carbonate water index no more than 8 /mg-ekv/l/2. Thus it is possible to achieve the effect of inhibiting scaling in thermal networks up to 90%.

However, in some regions in heating systems use local, the cheers of the water leaving the hot water boiler - 110-130oC. under these conditions, as shown by research to provide a high effect of inhibition using the above-described inhibitor fails.

One of the reasons for the decline of consumer properties of the inhibitor in harsh applications is the presence of salts of phosphorous and phosphoric acid in an amount up to 5%, resulting in high hardness water or at high temperature to the deposition of calcium phosphates and, as a consequence, to local overheating.

In the present invention proposes a new method of obtaining inhibitor deposits of mineral salts by the interaction of derivatives of ammonia, including ammonium chloride or waste production polyethylenepolyamines, with formaldehyde and phosphorous acid as such or a product of hydrolysis of phosphorus trichloride in an environment of diluted hydrochloric acid at elevated temperature, followed by neutralization of the resulting solution with sodium hydroxide to pH 6,51,0, wherein the process is conducted at a molar ratio of reagents, ammonia /ammonium chloride/: formaldehyde : phosphoric acid 1,0: 2,35-2,65:2,2-2,4.

Inhibitor of deposits of mineral salts obtained by the proposed method is with znachitelnoi mixed salts of phosphorous and phosphoric acids.

Below are examples 1-4 getting inhibitor deposits of mineral salts on the proposed method. Table 1 shows the results of the study of the composition of the samples obtained in examples 1-4, as well as for comparison of the composition of the prototype by the method of NMR spectroscopy31P.

Example 1. In enameled reactor equipped with a reflux condenser, jacket heating and cooling, a stirrer and a thermocouple, load 423 kg 64% aqueous solution of phosphorous acid /3,3 mol H3PO3/ and 35.6 kg of concentrated /36%/ hydrochloric acid. The mixture of acids is heated under stirring up to a temperature of 55-60oC and at this temperature load consistently within 0.3-0.5 h of 80.3 kg of ammonium chloride /to 1.5 mol based on 100% product and within 1-1 .5 hours of 286.2 kg of a 37% solution of formaldehyde /3,53 mole of CH2O/.

The molar ratio of NH4Cl:CH2O:H3PO31,0:2,35:2,2.

Then the reaction solution is heated under stirring up to a temperature of 102-105oC, stirred at this temperature for 2.5-3 h, cooled to 35-40oC and at this temperature, neutralized 42% aqueous solution of sodium hydroxide to a pH 6,51,0. Consumption of rest the lei.

Example 2. All components, equipment, order, load, temperature and time regimes similar to those in example 1.

Charged to the reactor to 422.8 kg 64% aqueous solution of phosphorous acid /3,3 mol H3PO3/; 35,6 kg of concentrated hydrochloric acid; of 80.3 kg of ammonium chloride /to 1.5 mol based on 100% product and 294,3 kg of a 37% solution of formaldehyde /3,63 mole of CH2O/.

The molar ratio of NH4Cl:CH2O:H3PO31,0:2,42:2,2.

Example 3. In enameled reactor equipped with a reflux condenser, jacket heating and cooling, a stirrer and a thermocouple, load 94,4 kg 27% aqueous ammonia /a 1.5 mol of NH3/ and with stirring and cooling /30oC/ gradually over a period of 0.5-1.0 h add 321,1 kg of a 37% aqueous solution of formaldehyde /3,96 mole of CH2O/. To the resulting solution was added gradually with stirring 494.5 /kg to 3.6 mol/ trichloride phosphorus, maintaining the temperature of the reaction mass not exceeding 40-45oC cooling and feed speed of the latter. Boot time trichloride phosphorus is 1.0 to 1.5 hours

The molar ratio of NH4Cl:CH2O:H3PO31,0:2,64:2,4.

On achemasia at this temperature of 2.5-3.0 h, cooled to 35-40oC and at this temperature, neutralized 42% aqueous solution of sodium hydroxide to a pH 6,51,0. The consumption of the alkali solution is 6555 kg

After cooling, get 11705 kg inhibitor deposits of mineral salts.

Example 4. All components, equipment, order, load, temperature and time regimes similar to those in example 3.

In reactor load 94,4 kg 27% aqueous ammonia /a 1.5 mol of NH3/, 347,8 kg of a 37% aqueous solution of formaldehyde /4,3 mole of CH2O/, 536,2 kg /3,9 mol/ phosphorus trichloride.

The molar ratio of NH4Cl:CH2O:H3PO31,0:2,86:2,6.

As can be seen from table 1 when changing the molar ratio of the reagents, interact in the reaction process, the ratio changes NTF, MIDP and other components in the mixture of inhibitor deposits of mineral salts. The concentration of salts of phosphorous and phosphoric acids is reduced from 4-5% in the composition obtained by the prototype, up to 1.5-2% in the new composition, and the content MIDP increased from 1.0% in the structure of the prototype to 6.0-7.0% in the new structure.

The following examples 5 and 6 show the results of tests of inhibitory treatment capacity of 200 cm3pour 100 cm3water carbonate index 15 /hardness of 5 mEq/l, alkalinity of 3 mEq/l/ and is maintained at 130oC for 2 h with the sample inhibitor. After the experience by standard methods to determine the change in the value of carbonate index and the amount of deposits formed on the walls of the autoclave (SU 1636758, 1991).

The efficiency calculated by the formula:

< / BR>
where A1- the amount of sediment in the control experiment, g/m2h;

A2- the amount of sediment after the experience with the sample inhibitor, g/m2h

Example 6. Tests of inhibitory capacity of the samples were carried out as in example 5. The test water is carbonate index 20 /water hardness 5 mEq/l, alkalinity of 4 mEq/L./ temperature test 140oC. the Efficiency is determined by the formula shown in example 5.

The results are given in table 3.

As is seen in tables 2 and 3 results, the inhibitor obtained when the molar ratio of the initial reagents, adopted in the prototype, for water with high carbonate index at high temperatures in the range of 130-140oC is ineffective.

To provide a high effect ingabire, is received when offered a molar ratio of initial reagents - ammonia: formaldehyde: phosphoric acid 1,0:2,35-2,65:2,2-2,4. The effectiveness of inhibition of scaling increased by more than 1.5 times and reaches 80-90%.

A further increase in the molar ratio of the initial reagents /example 4/ is not accompanied by improvement in inhibitory ability, but requires increased expenditure coefficients for raw materials and therefore impractical.

Thus, the proposed method for inhibiting deposits of mineral salts, characterized in that the reaction process is carried out at a molar ratio of initial reagents - ammonia:formaldehyde:phosphoric acid 1,0:2,35-2,65:2,2-2,4, leads to a new composition, which increases the salt content MIDP and is significantly reduced in comparison with the prototype of the salt content of phosphorous and phosphoric acids. Thus obtained in the proposed conditions, the inhibitor provides a high effect of inhibition even in the toughest conditions: when carbonate index of water 15-20 /mg-ekv/l/2and the outlet water temperature from the boiler to 140oC.

The method of obtaining inhibitor sediments monolitiniame, with formaldehyde and phosphorous acid as such or a product of hydrolysis of phosphorus trichloride in an environment of diluted hydrochloric acid at elevated temperature, followed by neutralization of the resulting solution with sodium hydroxide to a pH of 6.5 to 1.0, wherein the process is conducted at a molar ratio of the initial reagents - ammonia : formaldehyde : phosphoric acid 1,0 : 2,35 - 2,65 : 2,2 - 2,4.

 

Same patents:

The invention relates to a method for producing a solid disodium salt of nitrilotriethanol acid (NTF) by neutralizing the solution NTF - acid with sodium hydroxide to pH 2.5 and 3.4

The invention relates to a method of removing phosphorus-containing wastes generated upon receipt of salts of omega-amino-(C2-C6)alkylidene-1-hydroxy-1,1-bisphosphonic acids, which includes the stages of: a) contacting the aqueous medium after separation of the salts of omega-amino-(C2-C6)alkylidene-1-hydroxy-1,1-bis-phosphonic acid with a compound of chloride of calcium, taken in an amount of 2-10 wt

The invention relates to a new containing Quaternary nitrogen compounds of phosphonates and their pharmaceutically acceptable salts and esters having the General structure I

The invention relates to new tizamidine pyridinylmethyl acids f-ly R2-Z-Q-(CR1R1)n-CH[P(O)(OH)2]2(I) where R1-H, -SH, -(CH2)mSH or-S-C(O)-R3, R3- C1-C8-alkyl, m = 1 - 6, n = 0 to 6, Q is a covalent bond or-NH-, Z - pyridinyl, R2- H, -SH, -(CH2)mSH, -(CH2)mS-C(O)R3or-NH-C(O)-R4-SH, where R3and m have the above meaning, R4- C1-C8-alkylen, or their pharmaceutically acceptable salts or esters

The invention relates to a derivative of guanidine-1,1-bis phosphonic acid, method for their production and to their use
The invention relates to the field of chemistry of organophosphorus compounds, in particular, to methods for producing uranyl trinational the salt postemergency acid, used in medicine and cosmetics as an anti-virus drug

FIELD: organophosphorus compounds, medicine.

SUBSTANCE: invention relates to new biologically active phosphonate compounds. Invention describes phosphonate compound of the formula:

wherein R1 and R'1 represent independently hydrogen atom (-H) substituted possibly with -O-(C1-C24)-alkyl, -O-(C1-C24)-alkenyl, -O-(C1-C24)-acyl, -S-(C1-C24)-alkyl, -S-(C1-C24)-alkenyl or -S-(C1-C24)-acyl wherein at least one among R and R'1 doesn't represent -H and wherein indicated alkenyl or acyl comprise from 1 to 6 double bonds; R2 and R'2 represent independently -H substituted possibly with -O-(C1-C7)-alkyl, -O-(C1-C7)-alkenyl, -S-(C1-C7)-alkyl, -S-(C1-C7)-alkenyl, -O-(C1-C7)-acyl, -S-(C1-C7)-acyl, -N-(C1-C7)-acyl, -NH-(C1-C7)-alkyl, -N-((C1-C7)alkyl)2, oxo-group, halogen atom, -NH2, -OH or -SH; R3 represents phosphonate derivative of nucleoside or biphosphonate; X represents compound of the formula:

L represents a valence bond or a bifunctional binding molecule of the formula: -J-(CR2)t-G- wherein t is a whole number from 1 to 24; J and G represent independently -O-, -S-, -C(O)O- or -NH-; R represents -H, unsubstituted or substituted alkyl or alkenyl; m means a whole number from 0 to 6; n = 0 or 1. Also, invention describes pharmaceutical compositions comprising phosphonate compounds, method for treatment of osteoporosis in mammal, method for increasing mineral osseous density, method for prophylaxis of apoptosis of osteoblasts and osteocytes in mammal, method for treatment of viral infection in mammal, method for treatment of growing neoplasm in mammal and method for proliferation of cells. Invention provides preparing new compounds eliciting useful biological properties.

EFFECT: valuable medicinal properties of phosphonate compounds.

17 cl, 2 dwg, 7 tbl, 21 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to the improved method for preparing N-phosphonomethylglycine. Method involves interaction of derivative of hexahydrotriazine of the formula (II):

wherein X represents CN, COOZ, CH2OY and others; Z and Y represent hydrogen atom and others with triacylphosphite of the formula: P(OCOR3)3 (III) wherein R3 means (C1-C18)-alkyl or aryl that can be substituted. The prepared product is hydrolyzed and (if X represents CH2OY) oxidized. The proposed method is a simple in realization, economy and provides high degree of the end product purity.

EFFECT: improved preparing method.

19 cl, 11 ex

FIELD: chemical technology.

SUBSTANCE: invention relates to a selective method for removing chloride as NaCl from waste in method for preparing N-phosphonomethyliminodiacetic acid. The waste flow is neutralized with NaOH to pH value about 7, water is evaporated from flow of neutralized waste under atmospheric or lower pressure at temperature from 40°C to 130°C until to precipitation of NaCl. The precipitate is filtered off at temperature from 35°C to 110°C to isolate NaCl from filtrate and NaCl is washed out with saturated saline solution. Invention provides effective removal of NaCl from waste in a method for manufacturing N-phoaphonomethyliminodiacetic acid.

EFFECT: improved treatment method.

7 cl, 2 ex

FIELD: organic chemistry, chemical technology, medicine.

SUBSTANCE: invention relates to acyclic nucleoside phosphonate derivatives of the formula (1): wherein means a simple or double bond; R1 means hydrogen atom; R2 and R3 mean hydrogen atom or (C1-C7)-alkyl; R7 and R8 mean hydrogen atom or (C1-C4)-alkyl; R4 and R5 mean hydrogen atom or (C1-C4)-alkyl possibly substituted with one or more halogen atoms, or -(CH2)m-OC(=O)-R6 wherein m means a whole number from 1 to 5; R6 means (C1-C7)-alkyl or 3-6-membered heterocycle comprising 1 or 2 heteroatoms taken among the group consisting of nitrogen (N) and oxygen (O) atoms; Y means -O-, -CH(Z)-, =C(Z)-, -N(Z)- wherein Z means hydrogen atom, hydroxy-group or halogen atom, or (C1-C7)-alkyl; Q (see the claim invention); its pharmaceutically acceptable salts or stereoisomers. Also, invention proposes methods for preparing compounds of the formula (1) and their using in treatment of hepatitis B or preparing a medicinal agent designated for this aim.

EFFECT: improved preparing method, valuable medicinal properties of compounds and agent.

16 cl, 10 tbl, 87 ex

FIELD: chemical technology of organophosphorus compounds.

SUBSTANCE: method involves preparing nickel (II) bis-(1-hydroxyethane-1,1-diphosphonate (1-)) by addition 1-hydroxyethane-1,1-diphosphonic acid in the concentration 0.2-4.5 mole/l to an aqueous solution containing nickel (II) in the concentration 0.1-2.0 mole/l and organic solvent mixing with water followed by crystallization of the end substance from the solution. Method provides preparing the pure homogeneous end product with high yield, and utilization of depleted electrolyte in nickel plating representing a toxic waste in galvanic manufacture.

EFFECT: improved preparing method.

11 cl, 1 tbl, 12 ex

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for preparing N-phosphonomethylglycine. Invention describes a method for preparing N-phosphonomethylglycine from an aqueous mixture containing dissolved N-phosphonomethylglycine, ammonium halides, alkali or earth-alkali metal halides and, optionally, organic impurities. Method involves (a) using a mixture with pH value from 2 to 8; (b) separation of mixture is carried out on a selective nanofiltration membrane, and retentate enriched with N-phosphonomethylglycine and depleted with halides and permeate depleted with N-phosphonomethylglycine are obtained, and (c) N-phosphonomethylglycine is isolated from retentate. Method provides preparing N-phosphonomethylglycine in simultaneous separation of halide salts.

EFFECT: improved preparing method.

13 cl, 5 dwg, 2 tbl, 2 ex

FIELD: organophosphorus compounds, chemical technology.

SUBSTANCE: invention relates to technology of organic substances, in particular, to the improved method for preparing copper (II) bis-(1-hydroxyethane-1,1-diphosphonate (1-)). The final copper (II) bis-(1-hydroxyethane-1,1-diphosphonate (1-)) is prepared by crystallization from aqueous solution with concentrations of copper salt (II) from 0.5 to 2.0 mole/l and 1-hydroxyethane-1,1-diphosphonic acid with concentration from 2.0 to 6.0 mole/l prepared by using copper-containing waste in galvanic and electronic engineering manufacture, or by using a semi-finished product from production of 1-hydroxyethane-1,1-diphosphonic acid. Invention provides reducing cost in production of copper (I) bis-(1-hydroxyethane-1,1-diphosphonate (1-)) in combination with retaining purity, expanded raw base for preparing the end product and utilization of manufacture waste.

EFFECT: improved preparing method.

9 cl, 1 tbl, 8 ex

FIELD: chemistry of organophosphorus compounds, agriculture, pesticides.

SUBSTANCE: invention describes bis-(diethylammonium)-dihydrogen-1-hydroxyethyl-1,1diphosphonate monohydrate of the formula (I) showing properties of stimulator of growth o agricultural root crop plants. Invention provides enhancing productivity of root crops beet and carrot and expanding assortment of agents for this designation.

EFFECT: valuable agricultural properties of agent.

1 tbl, 2 ex

FIELD: chemical technology.

SUBSTANCE: invention relates to the improved method for preparing bis-(1-hydroxyethane-1,1-diphosphonate(1-)) zinc (II). Method involves interaction of zinc-containing reagent and 1-hydroxyethane-1,1-diphosphonic acid in a solvent medium, crystallization of the end product from solution, separation of deposit from solution and drying the deposit. Method involves using water-soluble zinc (II) salt with anion of strong acid as a zinc-containing reagent and preparing the solution with the concentration of zinc (II) salt from 0.2 to 2.2 mole/l and the concentration of 1-hydroxyethane-1,1-diphosphonic acid from 0.4 to 5.0 mole/l. The end product prepared by proposed method can be used in preparing phosphonate electrolytes for galvanic zinc-plating, for preparing zinc-phosphate inhibitors of steel corrosion, as trace supplement to vitamin preparations and fodders for animals, as a zinc microfertilizer in agriculture and for preparing other compounds of zinc (II). Invention provides enhancing purity and uniformity of the end product, increasing its yield, improved technological effectiveness of process, utilizing toxic waste in galvanic manufacturing.

EFFECT: improved preparing method.

8 cl, 1 tbl, 6 ex

FIELD: chemical technology.

SUBSTANCE: invention relates to technology for synthesis of crystalline nitrilotrimethylphosphonic acid sodium salts. For synthesis of nitrilotrimethylphosphonic acid disodium salt monohydrate the method involves preliminary synthesis of nitrilotrimethylphosphonic acid by interaction of phosphorus trichloride, formaldehyde and ammonia or its derivative followed by neutralization with sodium hydroxide in the content in the reaction mass 46-54 wt.-% of nitrilotrimethylphosphonic acid and 6.0-16.0 wt.-% of hydrogen chloride up to pH value 2.5-4.5, and isolation of the end compound by crystallization. The mass part of the main substance in synthesized product is 88-95%, the content of chloride ions is 1.2-2.0%, yield is 50-60% as measured for PCl3. Synthesized compound is recommended for using as chelate compounds as a component of detergents, anti-rheological additive in drilling solutions, plasticizing agents for building concretes, in wine-making industry, as inhibitors of salt depositions in heat and power engineering and others fields.

EFFECT: improved method of synthesis.

2 tbl, 12 ex

Up!