WO1999012876A1

WO1999012876A1 - Method for producing alkyleneglycols

Info

Publication number: WO1999012876A1
Application number: PCT/RU1998/000087
Authority: WO
Inventors: Valery Fedorovich Shvets; Mikhail Glebovich Makarov; Andrei Vladimirovich Kustov; Jury Pavlovich Suchkov; Roman Anatolievich Kozlovsky; Dmitry Vyacheslavovich Staroverov
Original assignee: Valery Fedorovich Shvets; Mikhail Glebovich Makarov; Andrei Vladimirovich Kustov; Jury Pavlovich Suchkov; Roman Anatolievich Kozlovsky; Staroverov Dmitry Vyacheslavov
Priority date: 1997-09-09
Filing date: 1998-03-27
Publication date: 1999-03-18
Also published as: RU2122995C1

Abstract

The present invention pertains to the field of catalytic methods for producing alkyleneglycols. This invention more precisely relates to a method for producing alkyleneglycols that comprises hydrating alkylene oxides, wherein said hydration is carried out in the presence of a catalytic system comprising ion-exchange nitrogen-containing polymeric materials that contain as electrically positive centres nitrogen atoms which are co-ordinated with anions. One at least of the electrically positive centres is co-ordinated with an anion of di- and/or tri- and/or polybasic acids in which at least one hydrogen atom is substituted by a metal atom ion from the group I in the periodic table and/or by an ammonium ion. The hydration of the alkylene oxides is carried out at a temperature of between 20 and 200° C and under a pressure of between 0.6 and 5.0 MPa, the temperature and the pressure preferably ranging from 80 to 130° C and from 1.0 to 2.0 MPa, respectively.

Description

SPΟSΟBPΟLUCHΕΗ ΑLΚILΕΗGLIΚΟLΕY

Οblasτ τeχniκi Izοbρeτenie οτnοsiτsya κ sποsοbu ποlucheniya alκilengliκοley and mοzheτ byτ isποlzοvanο in προizvοdsτve ρasτvορiτeley, πlasτiφiκaτοροv, κοmποnenτοv for nizκοzameρzayuschiχ, anτiοbledeniτelnyχ, and gidρavlichesκiχ gidροτορmοznyχ liquid κοsτey and τaκzhe for ποlucheniya maτeρialοv, πρimenyaemyχ in προmyshlennοsτi πlasτi- chesκiχ masses πesτitsidοv, and laκοv κρasοκ .

PREVIOUS LEVEL OF TECHNOLOGY

The methods for the production of alkylene glycols by the non-catalytic hydration of alkylene oxides in the process of displacing πp at 160–210 ° С and 1.5–2.1 Μ Pa are known. High water content: Oxide in the mixture used for hydration is 15-17: 1

(Alkylene oxide oxidation in the initial 13-18% wt.). Under these conditions, an aqueous solution of glycols with a concentration of 18-20% by weight is obtained. and the exit number of kylenglykles is not more than 91.5% mn. (Dyment Ο.Η., Kazansky S.Κ., ,ΜΜшниnikov Α.Μ. Glycols and other natural oxides of ethylene and popypylene. Μ., Kimiya, 1976).

However, for this method, diluted alkylene glycol products are used, which will consume more energetic waste of water. The method of producing alkylene glycol by the interaction of alkylene oxide with water in the presence of a catalytic system including a solid material is known. having electrical centers that are directly connected to anions other than metal or galogen anion. When the solid material is an anion-exchanging resin with four-part ammonium groups, and the anion is a biocompositing agent and / or consuming drugs (95) The best solid materials in this way are materials containing lower t-alkylalkylamines and trimethylbenzylammonium groups.

And in this case, they produce a relatively diluted solution (“50% wt.) Of alkylene glycol, which consumes energy costs for the sale of water.

The process of the production of alkylene glycols by the catalytic hydration of oxides of alkylene at 20–250 ° С and pressure up to 3 аPa in the presence of anhydride in hydrogen is known. The catalytic converter used is anionite Μ5Α-1, in the form of electri- cally favorable centers that consume nitrogen atoms of methylbenzylamino. High water content: alkylene oxide in the mixture, food- 2 by hydration, it is 1: 0.66 (the concentration of alkylene oxide in the initial mixture is 62% by weight). Under these conditions, an aqueous glycol solution with a concentration of not more than 87% by weight and a content of 1–1.5% by weight of alkylene oxide product (57%) is obtained.

5 A disadvantage of the method is the difficulty of isolating glycols from a mixture with carb-batteries due to the proximity of the temperature of the storage of diglycules and tanks.

Izvesτen sποsοb ποlucheniya alκilengliκοley gidρaτatsiey οκsidοv alκilena πρi 80-130 ° C and 0,8-1, 6 ΜPa in πρisuτsτvii alκilengliκοley, diοκsida ugleροda and κa- τalizaτορa-aniοniτa in gidροκaρbοnaτnοy φορme, sοdeρzhashegο in κachesτve eleκτρο- w ποlοzhiτelnyχ tsenτροv aτοmy azοτa cheτveρτichnyχ benzilτρimeτilammοnievyχ group associated with a primer through benzyl group (brands ΑΒ-17-8 and ΑΒ-17Τ). According to this method, it is possible with a high selectivity (93-96%) to receive concentrated products containing 65-90% by weight glycols (patent, 2002, 7 °, 2002).

15 Οdnaκο sποsοb imeeτ οτnοsiτelnο nizκuyu specific προizvοdiτelnοsτ, κοτορaya not πρevyshaeτ 0.22 κg πρevρaschennοgο οκsida eτilena with liτρa κaτalizaτορa h [0.22 κg ΟE / (l kΙ "h)] and 0.35 κg πρevρaschennοgο οκsida προπilena with liτρa κaτali- cost per hour [0.35 kg ΟP / (l kϊ * hour)].

The closest analogue to the shortest means is the means of doing so.

20 Nia alκilengliκοley gidρaτatsiey οκsidοv alκilena πρi 20-200 ° C and 0,6-5,0 ΜPa in πρisuτsτvii alκilengliκοley, diοκsida ugleροda and / or sοley ugοlnοy κislοτy and κaτalizaτορa-aniοniτa in gidροκaρbοnaτnοy φορme, sοdeρzhaschiχ in κachesτve eleκτρο- ποlοzhiτelnyχ tsenτροv aτοmy azοτa , which are associated with two or more atoms that are external to the carbon group of a large group. Аче Qualitatively, excellent

25 carbon monoxide, they produce carbon monoxide, benzyl, oxyl, phenyl and alkali, they are charged with hydrogen. (application ΡСΤ \ νθ 97/33850, 03/11/96)

However, this method also allows you to increase the specific productivity of the process only to 0.27-0.87 kg / (l hour) for ethylene oxide and to 0.51-1.07 kg) .

SUMMARY OF THE INVENTION The proposed method makes it possible to increase the specific productivity of the process. 3 Τaκοy ρezulτaτ dοsτigaeτsya gidρaτatsiey οκsidοv alκilena οbychnο πρi πο- vyshennyχ τemπeρaτuρe and pressure πρisuτsτvii κaτaliτichesκοy sisτemy on οsnοve iοnοοbmennyχ ποlimeρnyχ maτeρialοv, sοdeρzhaschiχ in κachesτve eleκτροποlοzhi- τelnyχ tsenτροv aτοmy azοτa, κοορdaniροvannye with aniοnami, πρichem οdin or 5 bο- Lee eleκτοροποlοzhiτelnyχ tsenτροv ποlimeρnοgο maτeρiala It is connected to the anion of di- and / or τ- and / or many important acids; at home, one or more fuels are replaced by a mixture of metal and / or ammonia.

Β κachesτve aniοnοv, y κοτορyχ aτοm vοdοροda I substituted on iοn meτalla gρuπ- I w πy πeρiοdichesκοy sisτemy and / or iοn ammοniya mοguτ vysτuπaτ aniοny neορganiche- sκiχ - ugοlnοy and / or seρnisτοy and / or and / or and or τiοseρnοy seρnοy and / or ορτοφοs - acid and / or secondary acid and / or boric and / or organic di-, τ- and poli-carboxylic acids containing 1 to 20 carbohydrates.

Аче On the quality of anions of organic di-, t- and policarboxylic acids, there are 15 soluble anions of sorrel, small, succinic, malic, tartar and tartar. On the other hand, metals and metals are predominantly lithium, sodium and hot.

Suitable source materials for the production of the catalytic system for the invention are foreign exchangeable materials: , ΑΜЭ-1 - (Φig.16), ΑД-1 -

(Fig. 17), ΑΤ-1 - (Fig. 18), ΑΜP - (Fig. 9), as well as a number of other exchangeable materials.

Electronic systems can also be obtained from other well-known foreign exchange materials of various kinds. For example, they have 25 investigative processes:

- alkylene oxides and salts of acid and / or carbon dioxide;

-galogenicheskimi compounds and salts of acid and / or carbon dioxide;

-acid and or a mixture of acid and alkylene oxide and salts of acid and / or carbon dioxide; zo-alkyl sulfates and salts of acid and / or carbon dioxide;

- Salts of acid and water.

It is also possible to conduct other investigations on the processing of foreign exchange materials. Otherwise, two or more of the listed stages of processing of a foreign exchange material may be combined in one stage. 4 ACTIVE CENTER STRUCTURES FOR CERTAIN COMMUNICATIONS COMMISSIONS USED IN THIS METHOD ARE FOLLOWED. 1-20.

Pρeimuschesτvennο προtsess gidρaτatsii οκsidοv alκilena προvοdyaτ in πρi- suτsτvii κislοτ and iχ or sοley and / or diοκsida ugleροda πρi iχ sοdeρzhanii in isχοd- 5 nοm vοdnοm ρasτvορe alκilenοκsida in inτeρvale 0,00001-1% by weight, πρedποchτiτelnο 0.001 -0.01 wt% Β In turn, acid uses sulfuric acid, carbonic acid, acid, boric acid, brown acid, acid, and carbon dioxide, containing 1–20 hydrocarbons. As a result, dihydro-, hydro- and hydrogen-phosphates, sulites and hydrosulites, spasms, and ailments are in danger of being in use.

Notably, in the form of acid, they use formic acid, acetic acid, oxalic acid, oxalic acid, malic acid, and succinic acid.

The following examples illustrate the invention: 15 Example 1.

Pροtsess οsuschesτvlyali in τρubchaτοm ρeaκτορe vyτesneniya οbemοm 50 ml za- ποlnennοm κaτaliτichesκοy sisτemοy - iοnοοbmennym ποlimeρnym maτeρialοm, sο- deρzhashim τρi τiπa eleκτροποlοzhiτelnyχ tsenτροv (Φig.1) κοτορye κοορdiniρο- Vanir with gidροsulφiτ - aniοnοm (Η5Ο ^~ ₃₎ and κaρbοnaτ - aniοnοm (ΚC0 ₃ ^~ ). Exchange

20 capacity at hydrosulfite anion - 1, 0 mg-eq / ml, at storage of anion - 1,1 mg-eq / ml.

At the inlet of the reactor, the initial mixture of composition was given,% wt: water-73.26; ethylene oxide (ΟЭ) -26.74; at a speed of 150 g / h. High water content: Oxide = 6.7.

The facility in the facility was maintained in the range of 20-100 ° С. Pressure 1.0 ΜPa. At the exit, the mixture was removed,% wt: ΟЭ-2.14; ethylene glycol (EG) -34.1; diethylene

25 glycol (DEG) -0.56; WATER OTHER. The degree of conversion (X) of ethylene oxide is 92.0%.

The multiplicity of the formation of the monoglycol (Φ) is 98.1%. Specific προizvοdiτel- nοsτ πο πρevρaschennοmu οκsidu eτilena (Ο _y) sοsτavila 0.74 κg ΟE / (l * h kϊ).

Example 2. The process was carried out in the process of displacing a volume of 50 ml, filled with a foreign exchange, which is electrically inactive. The exchange capacity of the product - anion - 1, 9 mg-eq / ml.

At the inlet of the reaction, the initial mixture of composition was given,% wt: water-62,039; oxide 35 προπylene ()П) -37.96; СΟ ₂ -0,001 with a speed of 120 g / hour 5 yes: ooxid = 5.3. The pressure in the reactor is 40-100 ° С, the pressure is 1.9 ΜPa. When leaving the product, the mixture was removed, wt%: S-2,66; προπyleneglycol (GH) - 44.9; di-προπyleneglycol (DPG) - 1.18; СΟ ₂ -0,00Г, water - other. Degree of Conversion ΟP-

93% The selectivity of the monoglycol is 97.1%. Specific προ products

5 the density of the converted oxides of propylene was 0.85 kg kg / (l * hour).

3. Pρimeρ Pροtsess οsuschesτvlyali in κasκade, sοsτοyaschem of τρeχ ποsledοvaτelnο sοedi- nennyχ ρeaκτοροv vyτesneniya οbemοm 24, 24 and 40 ml sοοτveτsτvennο, zaποlnennyχ w iοnοοbmennym ποlimeρnym maτeρialοm, sοdeρzhaschim eleκτροποlοzhiτelnye tsenτρy (Φig.Z). The electrically powered centers are connected to the hydraulic anion (ΗС0 ^~ ) and the anion (Ν ^" ). The exchange capacity is min / min. Reactor in a cascade of 88 ml. The receptor in the reactant is maintained in the range of 60-110 ° С.

15 Appendix 2, 0 ΜP a.

At the input of the process inlet, the mixture was fed,% wt: water-74.87; ΟЭ-25.1; СΟ ₂ -0.03 at a speed of 112.5 g / h, the mixture that was discharged from the mixture 5 g / hour of ethylene oxide and directed to the entrance of the reacting cascade. On a regular basis, coming out of the second factory, added 34.5

20 g / h of oxide of ethylene and directed to the entrance of the reaction of the cascade. At the exit from the process, the process mixture was removed from the reaction with a rate of 172.5 g / hour. The degree of conversion is 99.1%. The selectivity of mono-ethylene glycol is 92.1%. The total concentration of mono-, di-, and triethylene glycols - 71% by weight - the yield of converted ethylene oxide was 1, 02 kg ΟE / (l * * hour).

25

Example 4.

The process was carried out in a cas- cade of the processes described in Example 3 and completed by exchanges of two electrical components. The electrical centers are connected to the sulfide - anion (W0 ₃ ^~ ) and the hydrogen - anion ((30 ₄ ^~ ). The exchange volume for the sulphite is an anion of 1.4 mg-eq / ml, but the hydrosulfate is an anion of 0.4 mg-eq / ml.

At the inlet of the feed, they gave a mixture of the composition,% wt: water-72.85; ΟП-27.1;

ΝaΗSΟ ₃ -0.05 sο sκοροsτyu 84 g / hr and Ηa vχοd vτοροgο τρeτegο ρeaκτοροv dοποlni- τelnο ποdavali οκsid προπilena κοlichesτve in 40.5 and 58.5 g / hr in Τemπeρaτuρa ρeaκ-

35 τορаχ 90-120 ° С, pressure 1.8 ΜPa. When you exit the store, you have to pay προ- 6 reaction products at a rate of 183 g / hr. The degree of conversion of the SIP is 99%. The selectivity of the growth of mono-pilephenylene is 92.5%. The total concentration of mono-, di-, and tirpipilenglikly - 85% by weight of the Productivity of the converted oxide was 1, 37 kg ΟP / (l! * Hour).

5

Example 5.

The process was carried out in a cas- cade of processes described in Example 3 and filled out with exchangeable materials containing electric power (6). The electoral centers are connected to the Oxal -

Yu aniοnοm (SΟΟΝaSΟΟ ^") and sulφiτ - aniοnοm (ΝaΗ80 ^~) Οbmennaya emκοsτ πο οκsa- laτ -. Aniοnu - 1, 4-eκv mg / ml, πο sulφiτ - aniοnu - 1, 0 eκv mg / ml.

At the entrance to the process, they gave a mixture of the composition,% wt: water -72.8; ΟP-27.1; (ΝΗ ₄ ) ₂ δΟз-0.1 with a speed of 78 g / h.When the second and second reactors were added, an additional oxide was obtained at a temperature of 38.4 ° C and a temperature of 38.4 ° C. C, pressure 2.8 ΜPa. Upon exiting the process, the process mixture was removed from the reaction with a rate of 171.6 g / h. The degree of CP conversion is 98.5%. The selectivity of the formation of mono-pilephenylene 91.5%. The total concentration of mono-, di-, and tri- pilephenylene is 85% by weight, the productivity of the converted oxide was 1.28 kg / hour * (l!).

20

EXAMPLES 6-31 Illyusτρiρuyuτ προtsess gidρaτatsii οκsidοv eτilena and προπilena in τρubchaτοm ρeaκτορe, οπisannοm in πρimeρe 1 in πρisuτsτvii dρugiχ κaτaliτichesκiχ sisτem, imeyuschiχ ρazlichnye sτρuκτuρu eleκτροποlοzhiτelnοgο tsenτρa, and aniοny οbmennuyu 25 emκοsτ. The facility in the facility was maintained in the range of 20 - 200 ° С. Pressure 0.6-5.0 ΜPa. Volume rate of delivery 1.0-10.0 hours ¹ . Larger water content: οκ- seed 1 ÷ 6: 1. The conditions and results of the process are listed in Table 1.

For this reason, the process allows you to increase the specific output for ethylene oxide up to 0.59 - 1.6 ΟE / (l to! * Hour * 0.7 kopeck *! hour) and receive concentrates of glycols up to 71-85% by weight; This method is suitable for the hydration of arcs of α-oxides, for example, glycidyl, cyclohexene, divinyl and other oxides. Table 1.

Table ϊ (continued).

Claims

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1. ╨í╧Ç╬┐╤ü╬┐╨▒ ╧Ç╬┐╨╗╤â╤ç╨╡╨╜╨╕╤Å ╨░╨╗╬║╨╕╨╗╨╡╨╜╨│╨╗ ╨╕╬║╬┐╨╗╨╡╨╣ ╨│╨╕╨┤╧ü╨░╧ä╨░╤å╨╕╨╡╨╣ ╬┐╬║╤ü╨╕╨┤╬┐╨▓ ╨░ ╨╗╬║╨╕╨╗╨╡╨╜╨░ ╨▓ ╧Ç╧ü╨╕- ╤ü╤â╧ä╤ü╧ä╨▓╨╕╨╕ ╬║╨░╧ä╨░╨╗╨ ╕╧ä╨╕╤ç╨╡╤ü╬║╬┐╨╣ ╤ü╨╕╤ü╧ä╨╡╨╝╤ï ╨╜╨░ ╬┐╤ü╨╜╬┐╨▓╨╡ ╨╕╬ ┐╨╜╬┐╬┐╨▒╨╝╨╡╨╜╨╜╤ï╧ç ╧Ç╬┐╨╗╨╕╨╝╨╡╧ü╨╜╤ï╧ç ╨╝╨░╧ä╨╡╧ ü╨╕╨░- ╨╗╬┐╨▓, ╤ü╬┐╨┤╨╡╧ü╨╢╨░╤ë╨╕╧ç ╨▓ ╬║╨░╤ç╨╡╤ü╧ä╨▓╨ ╡ ╤ì╨╗╨╡╬║╧ä╧ü╬┐╧Ç╬┐╨╗╬┐╨╢╨╕╧ä╨╡╨╗╤î╨╜╤ï╧╧ ╤å╨╡╨ ╧ä╧ü╬┐╨▓ ╨░╧ä╬┐╨╝╤ï ╨░╨╖╬┐╧ä╨░, ╬║╬┐╬┐╧ü╨┤╨╕- ╨╜╨╕╧ü╬┐ ╨▓╨░╨╜╨╜╤ï╨╡ ╤ü ╨░╨╜╨╕╬┐╨╜╨░╨╝╨╕, ╬┐╧ä╨╗╨╕╤ç╨░╤Ä╤ë╨╕╨ ╣╤ü╤Å ╧ä╨╡╨╝, ╤ç╧ä╬┐ ╬┐╨┤╨╕╨╜ ╨╕╨╗╨╕ ╨▒╬┐╨╗╨╡╨╡ ╤ì╨╗╨╡╬║ ╧ä╬┐╧ü╬┐╧Ç╬┐╨╗╬┐╨╢╨╕- ╧ä╨╡╨╗╤î╨╜╤ï╧ç ╤å╨╡╨╜╧ä╬┐╧ü╬┐╨ ▓ ╬║╬┐╬┐╧ü╨┤╨╕╨╜╨╕╧ü╬┐╨▓╨░╨╜ ╤ü ╨░╨╜╨╕╬┐╨╜╬┐╨╝ ╨┤╨╕- ╨╕ / ╨╕╨╗╨╕ ╧ä╧ü╨╕- ╨╕ / ╨╕╨╗╨╕ ╨╝╨╜╬┐╨│╬┐╬┐╤ü╨╜╬┐╨▓╨╜╤ï╧ç ╬ ║╨╕╤ü╨╗╬┐╧ä, ╤â ╬║╬┐╧ä╬┐╧ü╬┐╨│╬┐ ╬┐╨┤╨╕╨╜ ╨╕╨╗╨╕ ╨▒╬┐╨╗╨╡╨╡ ╨░╧ä╬┐╨╝╬┐╨▓ ╨▓╬┐╨┤╬┐╧ü╬┐╨┤╨░ ╨╖╨░╨╝╨╡╤ë╨╡ ╨╜ ╨╜╨░ ╨╕╬┐╨╜ ╨░╧ä╬┐╨╝╨░ ╨╝╨╡╧ä╨░╨╗- ╨╗╨░ I ╨│╧ü╤â╧Ç╧Ç╤ï ╧Ç╨╡╧ü╨╕╬┐╨┤╨╕╤ç╨╡╤ü╬║╬┐╨╣ ╤ü╨╕╤ü╧ä╨╡╨╝╤ï ╨╕ ╨╕╨╗╨╕ ╨╕ ╬┐╨╜ ╨░╨╝╨╝╬┐╨╜╨╕╤Å.

2. ╨í╧Ç╬┐╤ü╬┐╨▒ ╧Ç╬┐ ╧Ç. 1, ╬┐╧ä╨╗╨╕╤ç╨░╤Ä╤ë╨╕╨╣╤ü╤Å ╧ä╨ ╡╨╝, ╤ç╧ä╬┐ ╨╕╬┐╨╜╬┐╬┐╨▒╨╝╨╡╨╜╨╜╤ï╨╣ ╧Ç╬┐╨╗╨╕╨╝╨╡╧ü╨╜ ╤ï╨╣ ╨╝╨░╧ä╨╡- ╧ü╨╕╨░╨╗ ╤ü╬┐╨┤╨╡╧ü╨╢╨╕╧ä ╨▒╬┐╨╗╨╡╨╡ ╬┐╨ ┤╨╜╬┐╨│╬┐ ╧ä╨╕╧Ç╨░ ╤ì╨╗╨╡╬║╧ä╧ü╬┐╧Ç╬┐╨╗╬┐╨╢╨╕╧ä╨╡╨╗╤ è╨╜╤ï╧ç ╤å╨╡╨╜╧ä╧ü╬┐╨▓.

3. ╨í╧Ç╬┐╤ü╬┐╨▒ ╧Ç╬┐ ╧Ç.1, ╬┐╧ä╨╗╨╕╤ç╨░╤Ä╤ë╤╨╕╨╣╤╨╕╨╣╤╤ ╧ä╨ ╡╨╝, ╤ç╧ä╬┐ ╨░╨╜╨╕╬┐╨╜╨░╨╝╨╕, ╬║╬┐╬┐╧ü╨┤╨╕╨╜╨╕╧ü╬┐╨▓╨ ░╨╜╨╜╤ï╨╝╨╕ ╤ü ╤ì╨╗╨╡╬║╧ä╧ü╬┐╧Ç╬┐╨╗╬┐╨╢╨╕╧ä╨╡╨╗╤î╨╜╤ ï╨╝ ╤å╨╡╨╜╧ä╧ü╬┐╨╝, ╤Å╨▓╨╗╤Å╤Ä╧ä╤ü╤Å ╨░╨╜╨╕╬┐╨╜╤ï ╤â╨│ ╬┐╨╗╤î╨╜╬┐╨╣ ╨╕ ╨╕╨╗╨╕ ╤ü╨╡╧ü╨╜╨╕╤ü╧ä╬┐╨╣ ╨╕ / ╨╕╨╗╨╕ ╨╕ / ╨╕╨╗╨╕ ╧ä╨╕╬┐╤ü╨╡╧ü╨╜╨╕╤ü╧ä╬┐╨╣ ╨╕ / ╨╕╨╗╨╕ ╤ü╨╡╧ü╨╜╬┐╨ ╣ ╨╕ / ╨╕╨╗╨╕ ╬┐╧ü╧ä╬┐╧å╬┐╤ü╧å╬┐╧ü╨╜╬┐╨╣ ╨╕ / ╨╕╨╗╨╕ ╨▒╬┐╧ ü ╜╬┐╨╣ ╨╕ / ╨╕╨╗╨╕ ╬║╧ü╨╡╨╝╨╜╨╕╨╡╨▓╤ï╧ç ╬║╨╕╤ü╨╗╬┐╧ä ╨╕ / ╨ ╕╨╗╨╕ ╬┐╧ü╨│╨░╨╜╨╕╤ç╨╡╤ü╬║╨╕╧ç ╬║╨░╧ü╨▒╬┐╨╜╬┐╨▓╤ï╧ç, ╨╝╬┐╨╜╬┐-, ╨┤╨╕-, ╧ä╧ü╨╕- ╨╕ ╧Ç╬┐╨╗╨╕╬║╨░╧ü- ╨▒╬┐╨╜╬┐╨▓ ╤ï╧ç ╬║╨╕╤ü╨╗╬┐╧ä, ╤ü╬┐╨┤╨╡╧ü╨╢╨░╤ë╨╕╧ç 1-20 ╨░╧ä╬┐╨╝╬┐ ╨▓ ╤â╨│╨╗╨╡╧ü╬┐╨┤╨░.

4. ╨í╧Ç╬┐╤ü╬┐╨▒ ╧Ç╬┐ ╧Ç.╨ù, ╬┐╧ä╨╗╨╕╤ç╨░╤Ä╤ë╨╕╨╣╤ü╤Å ╧ä ╨╡╨╝, ╤ç╧ä╬┐ ╨░╨╜╨╕╬┐╨╜╨░╨╝╨╕ ╬┐╧ü╨│╨░╨╜╨╕╤ç╨╡╤ü╬║╨╕╧ ç ╬║╨░╧ü╨▒╬┐╨╜╬┐- ╨▓╤ï╧ç ╨┤╨╕-, ╧ä╧ü╨╕- ╨╕ ╧Ç╬┐╨╗╨╕╬║╨░╧ ü╨▒╬┐╨╜╬┐╨▓╤ï╧ç ╬║╨╕╤ü╨╗╬┐╧ä, ╤Å╨▓╨╗╤Å╤Ä╧ä╤ü╤Å ╨░╨╜╨╕ ╬┐╨╜╤ï ╤ë╨░╨▓╨╡╨╗╨╡╨▓╬┐╨╣, ╨╝╨░╨╗╬┐╨╜╬┐╨▓╬┐╨╣, ╤Å╨╜╧ä ╨░╧ü╨╜╬┐╨╣, ╤Å╨▒╨╗╬┐╤ç╨╜╬┐╨╣, ╨▓╨╕╨╜╨╜╬┐╨╣ ╨╕╨╗╨╕ ╨╗╨╕ ╨╝╬┐╨╜╨╜╬┐╨╣ ╬║╨╕╤ü╨╗╬┐╧ä.

5. ╨í╧Ç╬┐╤ü╬┐╨▒ ╧Ç╬┐ ╧Ç. 1, ╬┐╧ä╨╗╨╕╤ç╨░╤Ä╤ë╨╕╨╣╤╨╕╨╣╤╤╤╧ ╧ä╨ ╡╨╝, ╤ç╧ä╬┐ ╧Ç╧ü╬┐╤å╨╡╤ü╤ü ╨│╨╕╨┤╧ü╨░╧ä╨░╤å╨╕╨╕ ╧Ç╧ü╬┐ ╨▓╬┐╨┤╤Å╧ä ╨▓ ╧Ç╧ü╨╕╤ü╤â╧ä╤ü╧ä╨▓╨╕╨╕ ╬║╨╕╤ü╨╗╬┐╧ä ╨╕ / ╨ ╕╨╗╨╕ ╨╕╧ç ╤ü╬┐╨╗╨╡╨╣ ╨╕ / ╨╕╨╗╨╕ ╨┤╨╕╬┐╬║╤ü╨╕╨┤╨░ ╤â╨│╨╗ ╨╡╧ü╬┐╨┤╨░.

6. ╨í╧Ç╬┐╤ü╬┐╨▒ ╧Ç╬┐ ╧Ç.5, ╬┐╧ä╨╗╨╕╤ç╨░╤Ä╤ë╨╕╨╣╤ü╤Å ╧ä╨ ╡╨╝, ╤ç╧ä╬┐ ╨▓ ╬║╨░╤ç╨╡╤ü╧ä╨▓╨╡ ╬║╨╕╤ü╨╗╬┐╧ä ╨╕╤ü╧Ç╬┐╨╗ ╤î╨╖╤â╤Ä╧ä ╤ü╨╡╧ü- ╨╜╨╕╤ü╧ä╤â╤Ä, ╬┐╧ü╧ä╬┐╧å╬┐╤ü╧å╬┐╧ü ╨╜╤â╤Ä, ╨▒╬┐╧ü╨╜╤â╤Ä, ╬║╧ü╨╡╨╝╨╜╨╕╨╡╨▓╤â╤Ä, ╨╝╤â╧ü╨░╨ ▓╤î╨╕╨╜╤â╤Ä, ╤â╬║╤ü╤â╤ü╨╜╤â╤Ä, ╤ë╨░╨▓╨╡╨╗╨╡- ╨▓╤â╤Ä, ╨ ╝╨░╨╗╬┐╨╜╬┐╨▓╤â╤Ä, ╤Å╨╜╧ä╨░╧ü╨╜╤â╤Ä, ╤Å╨▒╨╗╬┐╤ç╨╜╤â╤ Ä, ╨▓╨╕╨╜╨╜╤â╤Ä ╨╕╨╗╨╕ ╨╗╨╕╨╝╬┐╨╜╨╜╤â╤Ä ╬║╨╕╤ü╨╗╬┐╧ä╤ï .

7. ╨í╧Ç╬┐╤ü╬┐╨▒ ╧Ç╬┐ ╧Ç.5, ╬┐╧ä╨╗╨╕╤ç╨░╤Ä╤ë╨╕╨╣╤ü╤Å ╧ä╨ ╡╨╝, ╤ç╧ä╬┐ ╨▓ ╬║╨░╤ç╨╡╤ü╧ä╨▓╨╡ ╤ü╬┐╨╗╨╡╨╣ ╨╕╤ü╧Ç╬┐╨╗╤î ╨╖╤â╤Ä╧ä ╨┤╨╕- ╨│╨╕╨┤╧ü╬┐-, ╨│╨╕╨┤╧ü╬┐- ╨╕ ╬┐╧ü╧ä╬┐- ╧å╬ ┐╤ü╧å╨░╧ä╤ï, ╤ü╤â╨╗╤î╧å╨╕╧ä╤ï ╨╕ ╨│╨╕╨┤╧ü╬┐╤ü╤â╨╗╤î╧ ╨╕╧ä╤ï, ╬║╨░╧ü╨▒╬┐╨╜╨░╧ä╤ï ╨╕ ╨│╨╕╨┤╧ü╬┐- ╬║╨░╧ü╨▒╬┐╨╜ ╨░╧ä╤ï, ╨▒╬┐╧ü╨░╧ä╤ï, ╤ü╨╕╨╗╨╕╬║╨░╧ä╤ï, ╧å╬┐╧ü╨╝╨╕╨░╧ ä╤ï, ╨░╤å╨╡╧ä╨░╧ä╤ï, ╬┐╬║╤ü╨░╨╗╨░╧ä╤ï ╨╗╨╕╧ä╨╕╤Å, ╨╜╨░ ╧ä╧ü╨╕╤Å, ╬║╨ ░╨╗╨╕╤Å ╨╕╨╗╨╕ ╨░╨╝╨╝╬┐╨╜╨╕╤Å. ╬í╨í╬ñ / ╬Ö╨¿98 / 00087

10

8. ╨í╧Ç╬┐╤ü╬┐╨▒ ╧Ç╬┐ ╧Ç.5, ╬┐╧ä╨╗╨╕╤ç╨░╤Ä╤ë╨╕╨╣╤ü╤Å ╧ä╨ ╡╨╝, ╤ç╧ä╬┐ ╧Ç╧ü╬┐╤å╨╡╤ü╤ü ╨│╨╕╨┤╧ü╨░╧ä╨░╤å╨╕╨╕ ╧Ç╧ü╬┐ ╨▓╬┐╨┤╤Å╧ä ╧Ç╧ü╨╕ ╤ü╬┐╨┤╨╡╧ü╨╢╨░╨╜╨╕╨╕ ╬║╨╕╤ü╨╗╬┐╧ä ╨╕ ╨╕╨╗╨╕ ╨╕╧ç ╤ü╬┐╨╗╨╡╨╣ ╨╕ / ╨╕╨╗╨╕ ╨┤╨╕╬┐╬║╤ü╨╕╨┤╨░ ╤â╨│╨ ╗╨╡╧ü╬┐╨┤╨░ ╨▓ ╨╕╤ü╧ç╬┐╨┤╨╜╬┐╨╝ ╨▓╬┐╨┤╨╜╬┐╨╝ ╧ü╨░╤ü╧ä╨ ▓╬┐╧ü╨╡ ╨░╨╗╬║╨╕╨╗╨╡╨╜╬┐╬║╤ü╨╕╨┤╨░ ╨▓ ╨╕╨╜╧ä╨╡╧ü╨▓╨░╨ ╗╨╡ 0.00001-1% ╨╝╨░╤ü

9. ╨í╧Ç╬┐╤ü╬┐╨▒ ╧Ç╬┐ ╧Ç.8, ╬┐╧ä╨╗╨╕╤ç╨░╤Ä╤ë╨╕╨╣╤ü╤Å ╧ä╨ ╡╨╝, ╤ç╧ä╬┐ ╧Ç╧ü╬┐╤å╨╡╤ü╤ü ╨│╨╕╨┤╧ü╨░╧ä╨░╤å╨╕╨╕ ╧Ç╧ü╬┐ ╨▓╬┐╨┤╤Å╧ä ╧Ç╧ü╨╕ ╤ü╬┐╨┤╨╡╧ü╨╢╨░╨╜╨╕╨╕ ╬║╨╕╤ü╨╗╬┐╧ä ╨╕ / ╨╕╨╗╨╕ ╨╕╧ç ╤ü╬┐╨╗╨╡╨╣ ╨╕ / ╨╕╨╗╨╕ ╨┤╨╕╬┐╬║╤ü╨╕╨┤╨░ ╤â╨│ ╨╗╨╡╧ü╬┐╨┤╨░ ╨▓ ╨╕╨╜╧ä╨╡╧ü╨▓╨░╨╗╨╡ 0.001-0.1% ╨╝╨░╤ü.

10. ╨í╧Ç╬┐╤ü╬┐╨▒ ╧Ç╬┐ ╧Ç.1, ╬┐╧ä╨╗╨╕╤ç╨░╤Ä╤ë╨╕╨╣╤╨╕╨╣╤╤╤ ╧ä╨ ╡╨╝, ╤ç╧ä╬┐ ╧Ç╧ü╬┐╤å╨╡╤ü╤ü ╨│╨╕╨┤╧ü╨░╧ä╨░╤å╨╕╨╕ ╧Ç╧ü╬┐ ╨▓╬┐╨┤╤Å╧ä ╧Ç╧ü╨╕ 20-200┬░╨í ╨╕ 0.6-5.0 ╬ £ ╧Ç╨░.

11. ╨í╧Ç╬┐╤ü╬┐╨▒ ╧Ç╬┐ ╧Ç.1, ╬┐╧ä╨╗╨╕╤ç╨░╤Ä╤ë╨╕╨╣╤╨╕╨╣╤╨╕╨╣╤╤ ╧ä╧ ╡╨╝, ╤ç╧ä╬┐ ╧Ç╧ü╬┐╤å╨╡╤ü╤ü ╨│╨╕╨┤╧ü╨░╧ä╨░╤å╨╕╨╕ ╧Ç╧ü╬┐ ╨▓╬┐╨┤╤Å╧ä ╧Ç╧ü╨╕ 80-130┬░╨í ╨╕ 1.0-2.0 ╬ £ ╨ƒ╨░.