SU471025A1 - Method of producing phosphate cationite - Google Patents

Description

SUBSTANCE: invention relates to the field of production of phosphoric acid cytonites, which are highly resistant to ionizing radiation, based on new oil refining products - asphaltites. Dobro-process Obtaining ion exchangers based on carbon-graphite materials is economically feasible at low cost and wide availability.

A known method for the production of phosphoric acid of cation exchangers based on a copolymer of styrene and divinylbenzene by chloromethylation of a co-polymer followed by phosphorpolymerization in the presence of Frydel-Crafts catalysts, for example, CrF-2P, SF-1 cationites and others.

The disadvantage of these cation exchangers is their low radiation resistance.

In order to increase the radiation resistance of the cation exchanger, the Debei-Refining asphaltids, which are representatives of carbon-graphite materials, are used as an aromatic compound. Cation exchangers have an EOC up to 4.4 mg eq / g.

Synthesirovany phosphate cation exchangers are more resistant to deysgviyu radiation (in particular to y-radiation) compared to similar industrial ones; cation exchangers КФ-1, КРФ-5П, КРФ-2П, КРФ-10П СФ-1.

In connection with the use of ion exchangers in the production of radioactive isotopes, the problem of the synthesis of nuclear class ion exchangers possessing sufficient radiation resistance has become urgent.

Initial asphaltene concentrates are industrial products for deasphalting petroleum residues with benzine.

The most typical asphalt get 15 for Dobyn-process from tar. Asphaltites contain, wt%: asphaltenes 75-80; resins and residual oils 10-20. Asphaltenes and resins are fused aromatic and heterocyclic products of a hybrid structure containing, in wt.%: C 83-85; H 8-10; S 5-6; N 0.5-0.8. The added process is an oil deasphalting process, it is embedded. Rei in industry in the USSR.

Protective effect, asphaltites have 25 due to their spatial structure,

does not vary depending on the chemical composition, l

The asphaltites of the Processed process are highly condensed flat plates packed in packs. An analysis of microphotographs taken with an UEVM-100A electron microscope with magnification from 10,000 to 40,000 times shows that they have a clearly expressed layered structure that does not have a crystal cut. The layers have a constant thickness with an average transverse diameter of about 1 µm. In addition, hexagonal structures (average area 100 A °), similar to the graphite structure, were found. The calculated inter-layer spacing is approximately 3.6 A.

It is precisely because of its 4thic structure that asphaltites provide a protective effect against radiation like a sponge. In this case, the protective effect is not only burned out by the presence of ng electrons, as in any aromatic ring, but the dissipation of the energy of the emission of aromatic molecules is not only along the plane of the plate, but also in the volume of the pack. This feature of the Doben process asphaltites makes them different from all other classes of aromatics that were previously used to produce ion exchange materials.

The positive effect created by the use of asphaltite of the Doben-process as cation exchanger matrices is enhanced by the fact that they are production waste.

petroleum products, and the cost of asphaltite is significantly lower than the cost of polymers used as matrices of rigid phosphate cation exchangers.

The introduction of ionogenic rpymt is carried out by chloromethylation of asphaltites, followed by phosphorylation in the presence of Friedel Crafts catalysts.

To convert the phosphine group to the phosphonic cationite, it is oxidized. Chloromethane asphaltites are made by known methods.

Phosphorylation of chloromethylated asphaltites (XMA) is carried out in 10-fold and the life of phosphorus trichloride from the catalyst of Friedel Crafts catalyst, which are phosphorylated according to the degree of phosphorus in the following series of Resection Ace Vg Aes es 1ps,

The optimal conditions for phosphorylation are the ratio XMA: PCIjrSnCU 1:10: (0.26-0.52) weight parts, temperature 35-60 ° C, time 1-2 hours.

Optimal oxidation conditions: concentration and H NOa 20-25%, time 2-24 hours, temperature

20-60 ° C. The phosphate cation exchanger obtained under optimal conditions has two dissociation constants at pH 4-5 and pH 10-11, which testifies to two hydroxyl groups.

. The resulting phosphate cation exchangers are irregularly shaped polydisperse grains with sizes of 0.1-0.3 mm, density of 1.06-1.08 g / cm, humidity 20% and swelling in water 30-40%. The static exchange capacity of cation exchangers is 0.1 n. NaOH is 1.7-4.4 mg. eq / g (pH range 4-11). Ionites in Na - and H-forms were irradiated with y-radiation () in a dry form and in the form of 0.1 n. NaOH and HCl.

The test results showed that in the dose range of 1–50–10 rad, the synthesized ion exchangers in any form do not lose their external form and exchange capacity in all the studied media. In contrast, the exchange capacity increases upon irradiation by an average of 1030%.

The most typical operating environments for cation exchangers are the neutral medium or the medium with slightly expressed acidity, which occurs during the sorption of a part of the cations, and the alkaline medium.

In the process of ion exchange, the H-form of the cation exchanger transforms into the N a-form. Therefore, it is most important to conduct studies of the me-form of the cation exchanger in alkaline solution.

The most common phosphoric acid polystyrene cation exchangers, such as SF-1, 1SRF-5H, KRF-2P, in the E-form at a dose of 2-10 rad in 0.1 H. NaOH completely dissolve and become useless. When irradiated in water, the same cation exchangers dissolve at a dose of 3.5-10 rad. The cation KF-1 (Na-form) when irradiated at 0.1 n. NaOH (5-13-10 rad) loses the exchange capacity by 8-11.5%.

The table presents the properties of the cation exchangers of the H- and Na-forms after irradiation.

One of the reasons for the dissolution of phosphoric acid polystyrene cations is a significant amount of ionogenic groups, which leads to their absorption of a large amount of water in a swelling state. Therefore, katonitov become highly sensitive to the action of radiation.

Thus, the synthesized phosphate cation exchangers on the basis of new petroleum refining products — Dobenprossss asphaltites in the Na and H-forms are more efficiently controlled by the effects of radiation at low and high doses. They do not lose their insolubility and ability to ion exchange at doses (up to 5-10 rad), twice the doses at which polysyrhenic cation exchangers exist (2-3.5-1 The positive property of the synthesized cationioites is a very small loss value in weight not exceeding 5%. Obviously, the number of introduced new groups is optimal for obtaining radiation-resistant ion exchangers. Example 1. In a three-necked flask, sleep & agitator, thermometer and reflux cooler, 13.1 g (1 fan) of asphaltite and add 6.13 g (0.48 parts by weight) of ThCl2 solution in 13 g (10 parts by weight) of a-chlorodamethyl ether. The reaction is carried out for 1.5 h of gf 57. Chloromethylated asphaltite (XMA) is washed until no SP (sample AgNOj) and dried to constant weight. The chlorine content determined by the Sheniger method is 12%. 1.52 g of XMA is loaded into an ampoule, where a solution of 0.5 mol (0.065 parts by weight) A1C1e is placed in 10 ml (10 parts by weight) PC 1z The injected ammonia is placed in the agitator, the reaction is carried out for 30 minutes at 50 ° C, after which the ampoule is cooled in an ice bath. The contents of the ampoule are transferred to a filter, washed until neutral, and dried to constant weight. SOY 0.1 n. NaOH 0.5 mEq / g. The cation exchanger obtained is oxidized at 60 ° C for 4 hours with 25% NMO3. SOY after oxidation of 0.1 n. NaOU 0.8 MGEV / H. PRI mme R 2. It differs from Example 1 in that “1.52 g of XMA is phosphorylated by 2 mol (0.267 wt. 4) A1Cl3 in 10 ml (10 parts by weight) of the RAC. OOE 0.1 n. NaOH 1.8 mg / g. Oxidation is carried out at 20 ° C for 24 hours at a rate of 0.1 n. NaOII 2.7 mEq / g. Example 3. It differs from Example 2 in that the oxidation is carried out for 4 hours at 60 ° C. The P content before oxidation is 3.38%, after oxidation 2.8%. SOY 0.1 n. NaOH, 3.2 mmoves / g. EXAMPLE 4: Differs from Example 1 in that 1.52 g of EMA is phosphorylated with 0.32 g (2 mol) of FeCl j in 10 ml of PCI j. SOY 0.1 n. NaOH 2 mEq / g. After oxidation, the cation exchanger has a SOY of 0.1 n. NaOH 2.3 mEq / g. EXAMPLE 5: Differs from Example 1 in that 1.52 g of XMA is phosphorylated with a solution of 0.52 g (2 mol) of SnCIa in 10 ml of PCL3. SOY 0.1 n. NaOH 2.5 mEq / g. After oxidation, the cation exchanger has a SOY of 0.1 n. NaOH 4.4 mEq / g. Content R 10%.

 Dose rate 230 rad / s, 50 ° C. The plus sign indicates the increment of the exchange capacity, the minus sign indicates the loss of the soybean.

7471025g

Claims (1)

Claims invention invention - Crafts aromatic compound, The method of obtaining phosphate cation-increasing radiation resistance of the cation exchanger, nitrate by chloromethylation and then pumping the aromatic compound is used phosphorylation in the presence of catalysts asphaltite Before the refinery ben-process. characterized in that