NL8303604A - METHOD FOR PREPARING AN AGENT FOR AGAINST SALES OF MINERAL SALTS - Google Patents

Description

N.O. 32096 1

Method for preparing an agent for preventing the deposition of mineral salts

The invention is generally in the field of the chemistry of organic phosphorus compounds and particularly relates to methods of preparing a mineral salt deposition agent which can be used in treatment systems 5. of water, mineral water desalination plants and in the production, transport and treatment of petroleum and natural gas *

A process is known for the preparation of an agent for combating the deposition of mineral salts by interaction of formaldehyde, phosphorous acid, a mixture of polyethylene-polyamine, monoethanolamine and arbamide, as well as ammonium chloride and / or hexamethylene tetramine , in a weight ratio of the components of 100: 55-75: 25--40: 50-70: 34-35 at a temperature of 98 to 100 ° C (Compare Russian inventor certificate No. 719,970).

This method is disadvantageous in that the obtained agent has only a very little protective effect against the deposition of mineral salts. In addition, too high a temperature is used in the synthesis according to this method.

A method which most closely approximates the method according to the invention as regards the technical essence and the result obtained concerns the preparation of an agent for combating the deposition of mineral salts, wherein formaldehyde is reacted with phosphorous acid and containing a nitrogen condensation product obtained by interaction of dichloroethane and aqueous ammonia at a temperature of 110 to 135 ° C. The above condensation product has the following composition: hydrochloride of polyethylene polyamines 38 to 70 wt% ammonia 0.1 to 1.0 wt% ammonia chloride 1.0 to 6.0 wt% water 25 to 27 wt%.

The preparation of the agent is carried out at a temperature of 98-100 ° C in dilute hydrochloric acid, after which the resulting solution is made basic with a sodium hydroxide solution until a pH value of 3.6-3.9 is obtained (Compare Russian inventors certification. cate 726.123).

However, this method is disadvantageous in that high temperatures are required for carrying it out 8303604 2. In addition, the mineral salt deposition agent produced by this method is insufficiently effective when used to stabilize unsaturated solutions of mineral salts.

The present invention generally aims at avoiding the drawbacks described above.

In particular, the present invention provides a method which makes it possible to produce an inhibitor which ensures a great protective effect against the deposition of mineral salts and which can be carried out at a lower temperature.

This object is achieved in that, according to the invention, a method is proposed for preparing an agent for combating the deposition of mineral salts, wherein in this method formaldehyde, a phosphorus-containing compound and a nitrogen-containing condensation product at elevated temperature in an aqueous medium, according to the invention using phosphorus trichloride as the phosphorus-containing compound and as the nitrogen-containing condensation product the product obtained by interacting epichlorohydrin and aqueous ammonia at 5- 20 ° C, wherein the ratio of the reaction materials is in the range between 1: 5 and 1:15, followed by treatment of the reaction mass with an alkali metal hydride used in the amount of 1.0 to 1.1 moles per mole epichlorohydrin and the unreacted ammonia are distilled off, the product following the following The composition has: mixture of 1,3-diaminopropanol-2 and a derivative of 1,3-diaminopropanol-2 with the general formula of the formula sheet,

where n means 2 - 5 ................ 3-33 wt

30 alkali metal chloride ................ 2 - 25 wt

water supplemented to ................ 100 wt

wherein 225-300 parts by weight of formaldehyde and 400-500 parts by weight of phosphorus trichloride are used per 100 parts by weight of a mixture of 1,3-diamino-propanol-2 and a derivative of 1,3-diaminopropanol-2 with the general formula of the formula sheet and the process is carried out at a temperature of 35-50 ° C.

The protective effect obtained with the inhibitor produced according to the known method (Russian inventor certificate 726.123) is only 38.4%, while the inhibitor prepared according to the method of the invention has a protective effect of 47.7-78 .6% reading 8303604 φ «.

3 vert.

In addition, the method of preparing a mineral salt inhibitor according to the invention advantageously differs from the known methods in that it consumes less energy. For example, according to the process of the inventor certificate 726,123, dichloroethane interacts with ammonia at 110 to 135 ° C, while according to the process of the invention, the reaction of epichlorohydrin with ammonia proceeds at a temperature of only 5-20 ° C.

Furthermore, in the known process for the preparation of a mineral salt inhibitor, the synthesis is carried out at 98 to 100 ° C, while such a synthesis is carried out at 35-50 ° in a method according to the invention G.

As previously mentioned, the nitrogen-containing condensation product is obtained by interaction of epichlorohydrin and aqueous ammonia at a molar ratio of the reaction materials in the range between 1: 5 and 1:15 and at a temperature of 5-20 ° C.

A lower ratio of epichlorohydrin and ammonia is undesirable because it may produce a water-insoluble polymer containing a significant amount of non-reactive tertiary nitrogen. A higher molar ratio of dichlorohydrin and ammonia results in non-productive costs of removing the excess aqueous ammonia during the synthesis of the inhibitor. Carrying out the reaction of epichlorohydrin with aqueous ammonia at a temperature below 5 ° C is undesirable because it adversely affects the formation rate of a mixture of amines (1,3-diaminopropanol-2 and a derivative of 1 3-diaminopropanol-2 of the general formula of the formula sheet), while the reaction temperature above 20 ° C is also disadvantageous due to the formation of an unwanted polymer product containing a large amount of tertiary nitrogen.

It has been indicated above that the interaction of form aldehyde, phosphorus trichloride and a nitrogen-containing condensation product (i.e. the method of phosphonomethylation) is conducted at 35-50 ° C, while 255-300 parts by weight of formaldehyde and 400-500 parts by weight of phosphorus trichloride per 100 parts by weight of a mixture of 1,3-diaminopropanol-2 and a derivative of 1,3-diaminopropanol-2 are taken from the formula of the formula. Conducting the phosphonomethylation process at a temperature below 35 ° C adversely affects the reaction rate and results in an incomplete phosphonomethylation of the above-mentioned amines only 8303504 V-4. On the other hand, carrying out the process above 50 ° C is also undesirable since the phosphonomethylation process is a highly exothermic process, so that controlling the process at elevated temperatures is very difficult. A smaller amount of formaldehyde and phosphorus trichloride with respect to a mixture of 1,3-d-aminopropanol-2 and a derivative of 1,3-diaminopropanol-2 than indicated above is undesirable since this will inevitably lead to incomplete phosphonomethylation of the amino groups in the the above amines, while a greater amount of formaldehyde and phosphorus trichloride relative to a mixture of 1,3-diaminopropanol-2 and a derivative of 1,3-diaminopropanol-2 than the above amount is undesirable since this leads to unjustified costs of starting materials.

The method according to the invention for preparing an inorganic salt inhibiting agent is carried out as follows.

Epichlorohydrin is added to aqueous ammonia at such a rate that the temperature of the reaction mass does not rise above a range of 5-20 ° C. The starting materials (epichlorohydrenes and ammonia) are used in a molar ratio of resp. 1: 5 to 1:15 used. Then, an alkali metal hydroxide, e.g., NaOH or KOH, is added in small amounts to the reaction mass to neutralize the hydrogen chloride formed. The molar ratio of epichlorohydrin and the alkali metal hydroxide in this case is 1: 1.1. The unreacted (excess) ammonia is then distilled off.

The result is a nitrogen-containing condensation product of the following composition: mixture of 1,3-diaminopropanol-2 and a derivative of 1,3-diaminopropanol-2 with the general formula of the formula sheet, where n means 2 - 5 ... ............. 3-33 wt. % alkali metal chloride ................ 2-25 wt% water supplemented to ................ 100 wt%

Then, the estimated amount of formaldehyde and phosphorus trichloride is added to the nitrogen-containing condensation product of the above composition. Once the reaction materials have been introduced into the reaction vessel, the temperature therein is raised to 35-50 ° C and the reaction mass is kept at this temperature for 3-6 hours.

In the following examples the invention is further elucidated.

8303604 »» 5

Example X.

513 kg 25% by weight of water-containing ammonia are placed in an enamelled reaction vessel equipped with a reflux condenser and apparatus for stirring, cooling, measuring temperature and pH, then 5 ° C 22.6 kg of epichlorohydrin are added, the mole ratio of epichlorohydrin to ammonia being 1:15. Then, to neutralize the hydrogen chloride formed, 9.77 kg of granular sodium hydroxide (the mole ratio of epichlorohydrin to sodium hydroxide being 1: 1) are introduced into the reaction vessel in small amounts and the reaction mass is stored for three hours. The unreacted (excess) ammonia is then distilled off to give 100 kg of a nitrogen-containing condensation product, which has the following composition: mixture of 1,3-diaminopropanol-2 and a derivative of 1,3-diaminopropanol-2 with the general formula of the formula sheet (80 Z - n - 1, 10 Z - n - 2.5 X - n - 3.3 Z -

n = · 4, 2 Z - n »5) ............... 22 wt

sodium trim chloride ............... 15 wt%

20 water supplemented to ............... 100 wt

Then, while stirring, 62.4 kg of formaldehyde and 100 kg of phosphorus trichloride (i.e., 283 parts by weight of formaldehyde and 454 parts by weight of phosphorus trichloride per 100 parts by weight of a mixture of 1,3-di-aminopropanol-2 and introduced a derivative of 1,3-diaminopropanol-2) into the reaction vessel. After this addition, the temperature in the reaction vessel is raised to 35 ° C and the reaction mass is kept at this temperature for 4 hours. As a result of the synthesis (the method of phosphonomethylation), 262 kg of the desired inhibitor are obtained.

Example II

116.5 kg of 10 wt% aqueous ammonia are charged to the same reaction vessel as in Example 1, then 3.08 kg of epichlorohydrin at 20 ° C are added, the mole ratio of epichlorohydrin to ammonia being 1:10. Then 1.39 kg of sodium hydroxide (the molar ratio to sodium hydroxide being 1: 1.05) are introduced into the reaction vessel in small amounts to neutralize the hydrogen chloride formed, and the reaction mass is allowed to stand for 4 hours, after which the excess ammonia is distilled off.

40 The result is 100 kg of a nitrogen-containing condensation product with the following composition: mixture of 1,3-diaminopropanol-2 and a derivative of 1,3-diaminopropanol-2 with the general formula of formula sheet 5 (75 Z - n - 1, 15 Z - n - 2, 5 Z - n «3,

3% - n = 4, 2% - n = 15 ...................... 3 wt

sodium chloride 2 parts by weight

water supplemented to 100 wt

Then, under stirring, 9 hg of formaldehyde and 15 kg of phosphorus trichloride (i.e. 300 parts of formaldehyde and 500 parts of phosphorus trichloride per 100 parts of a mixture of 1,3-diaminopropanol-2 with a derivative are introduced into the reaction vessel thereof). After the addition, the temperature in the reaction vessel is raised to 50 ° C and the reaction mass is allowed to stand for 6 hours. The synthesis yields 124 kg of the desired inhibitor.

Example III.

The reaction vessel of Example I is charged with 302 kg of 25% by weight water-containing ammonia, after which 33.9 kg of epichlorohydrin at 15 ° C are added thereto (the molar ratio of epichloro-hydrene to ammonia being 1: 5). Then 17 kg of sodium hydroxide (the molar ratio of epichlorohydrin to sodium hydroxide is 1: 1.1) are introduced into the reaction vessel in small amounts in order to neutralize the hydrogen chloride formed and the reaction mass is kept for 3 hours, after which the excess of ammonia is 25 removed by distillation.

The result is 100 kg of a nitrogen-containing condensation product of the following composition: mixture of 1,3-diaminopropanol and a derivative of 1,3-diaminopropanol-2 with the general formula of the formula sheet (86 Z-n-1 , 12 Z - n - 2, 1 Z - n - 3,

0.75 Z - n - 4, 0.25 Z - n - 5) ................ 33 wt

sodium chloride ................ 25 wt

water supplemented to ................ 100 wt.

Then, 85 kg of formaldehyde and 132 kg of phosphorus trichloride (i.e. 255 parts of formaldehyde and 400 parts of phosphorus trichloride per 100 parts of a mixture of 1,3-diaminopropanol-2 with a derivative are added to the reaction vessel with stirring thereof). After the addition, the temperature in the reaction vessel is raised to 40 ° C and the reaction mass is allowed to stand for 3 hours.

8303604 7

I

The synthesis yields 317 kg of the desired inhibitor.

Example IV.

The desired inhibitor is prepared in a manner similar to the method described in Example I, with the only tilt exception being that potassium hydroxide is used to neutralize the hydrogen chloride formed due to the interaction of epichlorohydrin and water containing ammonia.

As a result, 265 kg of the desired inhibitor are obtained.

Example V.

The reaction of epichlorohydrin with aqueous ammonia is carried out as in Example 1, but at 15 ° C. The phosphonomethylation process is carried out in the same manner as in Example 1 for 1-4 hours, but at 45 ° C.

The synthesis yields 264 kg of the desired inhibitor.

Example VI.

The reaction of epichlorohydrin with aqueous ammonia is carried out as in Example 1, but at 20 ° C for 4 hours.

The phosphonomethylation process is carried out as in Example 1 for 4 hours but at 50 ° C.

The synthesis yields 265 kg of the desired inhibitor.

Example VII.

The reaction of epichlorohydrin with aqueous ammonia is carried out as in Example II, with the only exception that the molar ratio of epichlorohydrin to ammonia is 1:15.

8.6 kg of formr aldehyde and 13.6 kg of phosphorus trichloride, ie 283 parts of formaldehyde and 454 parts of phosphorus trichloride per 100 parts of a mixture of 1,3-diaminopropanol, are then introduced into the reaction vessel with stirring. -2 and a derivative of 1,3-diaminopro panol-2 with the general formula of the formula sheet).

After the addition, the temperature in the reaction vessel is raised to 40 ° C and the reaction mass is allowed to stand for 4 hours.

The result is 122 kg of the desired inhibitor.

Example VIII.

The reaction of epichlorohydrin with ammonia containing water is carried out as in Example 1, but the molar ratio of epichlorohydrin to ammonia is 1:10 and the temperature is 20 ° C.

The phosphonomethylation process is carried out as in Example 1, but at 40 ° C for 4 hours.

The synthesis yields 260 kg of the desired inhibitor.

8303604

V

8 Ύ *

Example IX.

The reaction of epichlorohydrin with mater-containing ammonia is performed as in Example III, but at 20 ° C and the molar ratio of epichlorohydrin to ammonia is 1:15.

The phosphonomethylation process is carried out as in Example III at 40 ° C, but for 4 hours. In this case, 95 kg of formaldehyde and 150 kg of phosphorus trichloride are introduced into the reaction vessel (i.e., 300 parts by weight of formaldehyde and 500 parts by weight of phosphorus trichloride per 100 parts by weight of a mixture of 1,3-diaminopropanol-2 and a derivative of 1,3-diaminopropanol-2 with the general formula of the formula sheet.)

The synthesis yields 345 kg of the desired inhibitor.

The inhibitor prepared according to the method of the invention has been tested for the protective effect against the deposition of mineral salts, such as calcium sulfate and carbonate.

The protective effect provided by the inhibitor has been established by adding the inhibitor at a concentration of 10 mg / l (as a mixture of phosphonomethyl amines) to 750 ml of groundwater, to which minerals have been added.

For the implementation, 200 ml of mineral-containing groundwater were poured into a steel beaker, this water containing the inhibitor according to the invention in a concentration of 10 mg / l, after which part of the water was evaporated by heating. During evaporation, the remaining 550 ml of mineral water containing groundwater, to which the inhibitor has been added, has been continuously and gradually added to the beaker in order to keep the effective water volume therein constant (200 ml). The evaporation ratio is 275 in all tests. Groundwater containing minerals has been used with water having the following properties: density, g / cm ^ ...................... .. 1,055 30 total amount of minerals, mg-eq / 1 ... 2717,596 K ++ Na +, kg-eq / 1 ..................... .... 1149,022

Ca2 +, mg-eq / 1 ........................... 135,763

Mg2 +, mg-eq / 1 ......... 74,013

Cl ', mg-eq / 1 ............................ 1277,595 35 SO #', mg-eq / 1. .......................... 77,991 HCOO3, mg-eq / 1 ................ ... 0.196

For comparison, an inhibitor prepared according to the known method of the Russian inventor certificate 726.123 has been tested according to the same protocol.

40 The effective properties of the mineral salt depositing agents prepared according to the known working 8303604 -5? 9 method and the method according to the invention have been assessed on the basis of the amount of precipitate deposited on the walls of the beaker.

For comparison, a control test was performed using the above procedure without adding the inhibitor to the mineral-containing groundwater.

Determination of the protected effect obtained with the mineral salt depositing agent has been carried out by the following formula: 3, A ~ B. 100 »

10 A

where 3 is the protective effect provided by the inhibitor in percent A is the weight of the mineral salts deposited on the walls of the beaker in the control test (without 15 being the inhibitor) in g is B the weight of the mineral salts deposited on the walls of the beaker during the test with the inhibitor in g is In the table below, the values of the protective effect provided by the inhibitor according to Examples I - IX of the method according to the invention and the inhibitor, prepared according to the known method of the Russian inventor certificate 726.123.

8303604 "** ψ 10

Table*

Method for the preparation of an agent Inhibitor- Protective to counteract the deposit concentration, effect,% 5 of mineral salts_mg / 1_

Check - -

According to the known method of the

Russian inventor certificate 726,123 10.0 38.4

According to the method of the invention: Example I 10.0 69.6

Example II ditto 47.7

Example III ditto 69.9

Example IV ditto 70.0

Example V idem 62.8 15 Example VI idem 70.1

Example VII ditto 48.0

Example VIII ditto 64.0

EXAMPLE 9_IDEM_78.6 From the data in the above table it is clear that the agent prepared according to the method of the invention for combating the deposition of mineral salts is much better than the agent obtained according to the known method.

8303604

Claims (2)

11 m CONCLUSION. Process for preparing a mineral salt deposition inhibitor consisting of the interaction of formaldehyde, a phosphorus-containing compound and a nitrogen-containing condensation product in an aqueous medium at elevated temperature, characterized that the phosphorus-containing compound used is phosphorus trichloride and the nitrogen-containing condensation product is the product obtained by the interaction of epichlorohydrin and aqueous ammonia carried out at 5-20 ° C and the molar ratio of the reaction materials being in the range 1 : 5 and 1:15, followed by treatment of the reaction mass with an alkali metal hydroxide in an amount of 1.0 - 1.1 moles per mole of epichlorohydrin and removal of the unreacted ammonia by distillation, the product having the following composition: 15 mixture of 1,3-diaminopropanol-2 and a derivative of 1,3-diaminopropanol-2 with the general formula of the formula sheet, where n means 2 - 5 ............................... 3 -33 wt% alkali metal chloride ......................... 2 - 25 wt.% Water supplemented to .......................... 100 wt.%, With 255 - 300 wt. Formaldehyde and 400-500 parts by weight of phosphorus trichloride per 100 parts by weight of a mixture of 1,3-diaminopropanol-2 and a derivative of 1,3-diaminopropanol-2 with the general formula of the formula sheet are used, and the process is carried out at a temperature of 35-50 ° C. 8303604 '' [εΓΠΤ | : -4 JAM j Improvement of errata in the description associated with Patent Application No. 83.03604, proposed by the applicant, under the date 4 January 1984. 1, line 11: Change "arbamide" to "carbamide". 8, line 31: Change "kg-eq / 1" to "mg-eq / 1" ft 8303604