SU1342889A1 - Method of producing plasticizer for concrete mixes - Google Patents

Abstract

The invention relates to sulfonated mixtures, in particular the preparation of a plasticizer for concrete mixtures (BS). The goal is to simplify with cheapening the process of obtaining BS and their strength properties. Synthesis of plasticizer for BS is carried out by sulfonation of aromatic hydrocarbons - bottoms of phenol-acetone production using HiS04 (mass ratio 100-120: 100) at 130-150 s. The subsequent condensation of sulfomass with an aqueous (2.5–5%) formaldehyde solution (obtained from oversize water from the production of phenol formaldehyde resins) is carried out at 80–100 ° C. NaOH is neutralized. For sulphurization, it is advisable to use waste, formed as waste in the production of ion-exchange resins, strengthened by oleum. The use of these wastes S reduces the cost of BS and at the same time utilizes them with increasing strength properties of BS to 10.9-12.2 MPa (after 7 days) and 19.4 MPa (after 28 days) during normal storage. 2 з.п, ф-лы, 3 2 tab. (L

Description

 1342889

The invention relates to an improved method for producing an improved plasticizer that can be used in concrete mixtures.

The purpose of the invention is to simplify and reduce the cost of the process and increase the strength of concrete mixes, which is achieved using

Phenol water is used for the bottoms of the bottoms - waste from the production of phenol for- tone production, by carrying out sulfonation at a ratio of sulfuric acid to the bottoms residue of 100-100: and a temperature of 130-150 C and carrying out the condensation of sulfated mass with 2.5-5% aqueous formaldehyde solution at 80-100 C.

Preferably, the sulfonation is carried out with waste sulfuric acid, a waste product of ion-exchange resins, fortified with oleum, and an aqueous formaldehyde solution prepared using over-resin water from the production of phenol-formaldehyde resins is used for condensation.

The bottoms of phenol acetone production is produced according to specifications and has

em conditional viscosity at 80 ° C is not more than 8, water content is not more than 2.0%, mechanical impurities content is not more than 2.5%, discharging temperature in a closed crucible is not lower than 61 ° C, phenol containment is not less than 2.0%,

VAT residue phenolacetone production used in the examples, has the following chemical composition,%:

Phenol13,3

Paracumylphenol 16.5

Acetophenone dimethylphenylcarbinol 6, 9

ot-methylstyrene6,1

Linear dimer I ob-methylstyrene14, 9

Linear

dimer II

oi-methylstyrene2,3

Cyclical

dimer 4i-methylstyrene 3, 4

Unidentified products Else

Over-resin waters, which are waste products of phenol-formaldehyde resins, usually have the following characteristics:

Mass fraction brominated in terms of phenol,% 3.0-6.5

Mass fraction of free formaldehyde,% 2.0-5.0 In the preparation of the plasticizer, in the examples, a super-resin was used.

maldehyde resins for textolites,

containing 2.5% formaldehyde, with pH

7.3.

Sulfuric acid, waste production of cation exchangers, has

The following composition,%:

Content of sulfuric acid monohydrate 75-90 Content of aromatic water-soluble sulfonic acids of styrene, divinylbenzene, etc.

0.1-1.0 Content of dichloroethane 0.1-0.2

Rest

Water

In the preparation of the plasticizer, used sulfuric acid of the following composition was used in the examples,%: Content of sulfuric acid monohydrate90

Content of organic sulfo products 0.4 Content of dichloroethane 0.2 Content of water 19.4

The spent sulfuric acid is strengthened to a concentration of 96% by introducing 18% oleum into it.

The introduction of formaldehyde in the form of a 2.5-5% aqueous solution provides a linear polymer and eliminates the possibility of the formation of insoluble products at the condensation stage.

The decrease in the amount of sulfuric acid and the sulfonation temperature below their lower suggested limits does not ensure the complete sulfonation of all components of the bottoms residue of the phenol-acetone production.

An increase in the amount of sulfuric acid and a sulfonation temperature above their upper suggested limits leads to the oxidation of sulfonation products.

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Example 1. In a three-necked flask equipped with a stirrer, a reflux condenser and a thermometer, 100 g of the bottoms of phenol acetone production, 115.8 g of 95%

technical sulfuric acid, the temperature is raised to 140 ° C and maintained at it for 3-4 hours until the solubility of sulfomass in water at a ratio of 1:10. The obtained sulfomass is cooled to 50-55 ° C and 460.6 2.6% aqueous formaldehyde solution is introduced into it (a 2.6% solution is prepared preliminary from 428 g technical node and 32.6 g formalin). Then the temperature is increased to a boiling point of -100 ° C. The condensation is carried out for 1 hour, the reaction mixture is cooled to 70-80 ° C, neutralized by adding 193 g of 42% sodium hydroxide solution, cooled and decanted.

EXAMPLE 2. The method is carried out according to Example 1, but the distillation residue is sulphurised to 104.2 g of the fortified 20 mixture. At the same time, when using spent sulfuric acid, when plasticizer is applied, the C-3 thinner, made of 61 g of 90% spent sulfuric acid and 43.1 g of 18%

oleum. Sulfonation is carried out at 130 C,

possessing the same plasticizing properties, a decrease in the strength properties of the standard beta is observed; then 420 g of a 5% aqueous 25 ton mixture are introduced.

formaldehyde solution, condensation. The proposed method allows control at 90 ° C and neutralize the introduction of a plasticizer by eliminating the difficult and energy-intensive stage of stripping, trapping

Ddenia 144 g of 42% caustic soda.

Example 3. The method is carried out as in Example 1, but sulphurization of the wiring and regeneration of the aromatic gives 442.0 g of a 4% aqueous solution of the raw material after the sulphurization stage, formaldehyde, condensation is carried out at 80 ° C for 2 hours, 156 g of 42% sodium hydroxide.

phenol by the cumene method, over-resin waters from the production of phenol-formaldehyde resins and spent sulfuric acid from the production of cation exchangers.

The use of the bottoms of the phenol-acetone production allows the proposed method to not only make the method of production waste-free, but also comprehensively solves the process. Example 4. The method implements the problem of utilization of other waste products of example 1, but introduces 428 g of the superfluous substances - the bottom residue from the grinding water with a formaldehyde concentration of 2.5%.

EXAMPLE 5 The method is carried out as in example 1, but 427 g of a 5% formaldehyde solution prepared from 400 g of tar water and 27 g of 37% formalin are introduced.

Characteristics of the finished product

in examples 1-5 are given in table. 1. 4b significantly reduce the cost of the proposed

The vat residue contains 36.6% method, since the price of the vat residue

is 25-27 rubles / ton, while the price of naphthalene is 215- 190 rubles / ton. In addition, the proposed sulfonation products, or the gQ plasticizer product, gives a great deal of interaction with formaldehyde. ness concrete mixes than famous

Below are the tests for the proposed plasticizer and the known plasticizer for concrete. The C-3 thinner under the same conditions. Is1. The method for producing plasticizer concrete mixtures by sulfonating aromatic hydrocarbons from concentrated identifying substances, which are transferred to the final product, but it is not established in what form: either

(tab. 2). Formula

the invention

the tests are carried out on a standard concrete mix, the consumption of materials on

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Claims (3)

1 m of which is: cement 390 kg, sand 620 kg, rubble 1160 kg Sulfuric acid during heating. GENERA 195 l. Concrete mixes are prepared on Portland cement grade 400, gravel rubble with fractions of 5-10 mm in an amount of 33% and 10-20 mm in an amount of 75% by weight and river sand. Plasticizers are introduced in the amount of 0.7% (in terms of dry substance) of the weight of cement. In tab. 2 shows the results of tests of concrete mixes. From the data table. 2 that the proposed plasticizer can be used in concrete mixtures as plasticizing additive because meets all the requirements imposed on them, namely, it has a high plasticizing effect, without reducing the strength properties of concrete phenol by the cumene method, over-resin waters from the production of phenol-formaldehyde resins and spent sulfuric acid from the production of cation exchangers. The use of the bottoms of the phenol-acetone production allows the proposed method to not only make the method of production waste-free, but also comprehensively solves the problem of utilization of wastes from other productions - the bottoms from production (tab. 2). Formula the invention 55 sulfuric acid with heat 5134 by condensation of the obtained sulfomass with an aqueous solution of formaldehyde when heated, followed by neutralization with sodium hydroxide, and with the fact that hydrocarbons use bottoms of phenol-acetone production and sulfonation is carried out at a ratio of sulfuric acid to bottom distillation 100-120: 100 ppm. and a temperature of 130-150 C, and lead to condensation The content of the main substance is given from the total composition of the target product. table 2 Control sample (concrete mix without plasticizer) Concrete mix with a known plasticizer. C-3 thinner Concrete mix with the proposed plasticizer for example 0.7 0.7 9 2.5-5% water solution of formaldehyde at 80-100 ° C. 2. The method according to claim 1, which differs from the fact that the sulfonation is carried out with spent sulfuric acid, a waste product of ion-exchange resins fortified with oleum. 3. The method according to PP.1 and 2, about tl and h a y p and the fact that / ut condensation using an aqueous solution of formaldehyde, prepared using nadsselnogo water from the production of phenol-formaldehyde resins, Table 1 10.4 (106) 19.4 (197) 20 9.2 (94.3) 13.3 (139) 21 21 10.9 (112) 19.4 (198) 12.2 (124.2) 19.4 (197.5)