CN105566177A - Preparation method of barium diphenylaminesulfonate - Google Patents

Abstract

The invention relates to a preparation method of barium diphenylaminesulfonate. The preparation method comprises 1, adding 5kg of diphenylamine into a container, adding 4L of concentrated sulfuric acid into the container, installing a stirring device and a pressure reduction device, carrying out stirring heating to a temperature of 155-160 DEG C, starting the pressure reduction device and carrying out pressure reduction for water distillation, 2, after sulfonation, adding water into the sulfonation product, wherein the volume of the water is 1-2 times that of the sulfonation product, carrying out hydrolysis, keeping a temperature of 120-125 DEG C for 20-30min, carrying out stirring, fast pouring the mixture into boiling water of which the volume is 10-15 times that of the mixture, adding a barium hydroxide hot solution which has a concentration of 50wt% and has the weight is 5-7 times that of the mixed solution into the mixed solution, carrying out thermal insulation and precipitation for 1-2h, carrying out filtration and respectively collecting filter residues and filtrate, and 3, carrying out washing and drying to obtain a product. A diphenylamine sulfonation direct synthesis method is used and barium hydroxide is used as a SO4<2-> precipitating agent and an acid neutralizer so that deposition and neutralization are realized in one process and thus a cost is saved and work time is shortened.

Description

A kind of preparation method of barium diphenylaminesulfonate

Technical field

The invention belongs to indicator field in chemical reagent, especially a kind of preparation method of barium diphenylaminesulfonate.

Technical background

Barium diphenylaminesulfonate is white or light grey tiny plate crystal powder, sometimes with light blue.Be slightly soluble in cold water, be slightly dissolved in hot water, thermal degradation, but not melting, oxidizable in atmosphere, be mainly used in indicator and the oxidation-reduction indicator of ferrous salt.Existing preparation method obtains diphenylamine sulfonic acid by pentanoic through concentrated acid sulfonation, then obtains with barium carbonate neutralization.But product has a large amount of barium sulfate, make barium diphenylaminesulfonate content low, cause its sensitivity decrease, have a strong impact on use.Can only precipitated impurities vitriol with barium carbonate, the adjustment of solution acidity also handy a large amount of sodium carbonate neutralizes, and be finally converted into barium diphenylaminesulfonate again, complex process, man-hour is very long, and cost is very high.

Summary of the invention

The object of the invention is to overcome the deficiencies in the prior art part, a kind of preparation method of cost-saving, productive rate is high, product purity is high barium diphenylaminesulfonate is provided.

The object of the invention is to be achieved through the following technical solutions:

A preparation method for barium diphenylaminesulfonate, step is as follows:

(1) add 5Kg pentanoic in a reservoir, add the 4L vitriol oil, add whipping appts and reliever, be warming up to 155-160 DEG C, start reliever under stirring, decompression steams water, inspection sulfonation degree, if sulfonation is incomplete, increases decompression dynamics, steams water more fast;

(2) after sulfonation completes, add 1-2 times of volume water to be hydrolyzed reaction, at 120-125 DEG C of insulation 20-30 minute, add stirring, then pour into rapidly in the boiling water of 10-15 times of volume, add the 50wt% hydrated barta hot solution of 5-7 times of weight, insulation precipitation 1-2 hour, filter, collect filter residue and filtrate respectively;

(3) filter residue 2-3 times of volume hot-water soak 10min, then suction filtration, filtrate and front filtrate merge, and precipitation can discard, and filtrate is heated to 60-90 DEG C, adjust pH6-7 with 10wt% sodium carbonate solution; Heat filter, removing precipitation, adds the solid chlorine barium of 1-2 times of weight, stirs, is cooled to 5-20 DEG C, and have precipitation to generate, suction filtration precipitates, and washes away most of Cl with cold water ^-, after vacuum drying oven 80-100 DEG C drying, namely obtain product, measure its sensitivity, if defective, can purify once by recrystallization again.

And, described pentanoic: vitriol oil weight ratio=1:1.15-2.0.

Advantage of the present invention and positively effect:

1, the present invention adopts pentanoic through sulfonation direct synthesis technique, selects hydrated barta to be namely SO ₄ ^2-precipitation agent, be again acid neutralizing agent, precipitate and neutralize disposable completing, having saved cost, shortened man-hour.

2, in the present invention, during sulfonation, raw material ratio is pentanoic: H ₂sO ₄=1:1.5-2.0, greatly reduce H ₂sO ₄consumption, so both ensure that the complete of sulfonation, turn avoid the generation of diphenylamine-sulfonate, improve the productive rate of barium diphenylaminesulfonate.

3, the present invention controls sulfonation temperature (150-160 DEG C), is guaranteeing sulfonation reaction completely simultaneously, turn avoid temperature too high time form pentanoic-4,4-disulfonic acid barium and reduce quality product.

4, the present invention adds stirring in sulfonation process, and pentanoic is mixed with sulphonating agent, increases sulfonation speed, shortens sulfonation time, improves sulfonation efficiency, decreases operation steps, to be adapted to suitability for industrialized production

Concrete embodiment

In order to understand the present invention, below in conjunction with embodiment, the invention will be further described: following embodiment is illustrative, is not determinate, can not limit protection scope of the present invention with following embodiment.

Embodiment 1

A preparation method for barium diphenylaminesulfonate, step is as follows:

(1) in 10L triangular flask, add 5Kg pentanoic, add the 4L vitriol oil (>=98%), add whipping appts and reliever, under stirring, be warming up to 155-160 DEG C, start reliever, decompression steams 500-700ml water, and inspection sulfonation degree, if sulfonation is incomplete, increase decompression dynamics, steam 100-300ml water more fast;

(2) after sulfonation completes, add 4L water and to be hydrolyzed reaction, 120-125 DEG C of insulation 20 minutes, add stirring, then pour into rapidly in 50Kg boiling water, add 32Kg50wt% hydrated barta hot solution, insulation precipitation 1-2 hour, filters, and collects filter residue and filtrate respectively;

(3) filter residue 10L hot-water soak 10min, then suction filtration, filtrate and front filtrate merge, and precipitation can discard, and filtrate is heated to 60-90 DEG C, adjust pH6-7 with 10wt% sodium carbonate solution; Heat filter, removing precipitation, adds 5-6Kg solid chlorine barium, stirs, be cooled to 10-20 DEG C, have precipitation to generate, suction filtration precipitates, and washes away most of Cl-with cold water, after vacuum drying oven 80 DEG C of dryings, namely obtain product, measure its sensitivity, if defective, can purify once by recrystallization again.

Embodiment 2

A preparation method for barium diphenylaminesulfonate, step is as follows:

(1) in 20L triangular flask, add 8Kg pentanoic, add the 5-10L vitriol oil, be heated to 160 DEG C, in 1 hour, decompression steams 550ml water, and sample thief is chemically examined, and checks its sulfonation degree, if sulfonation is incomplete, steams 200-300ml water in decompression;

(2) after sulfonation completes, add 5L water and to be hydrolyzed translocation reaction, 125 DEG C of insulations 20 minutes, then pour in 50-60Kg water, be heated to boil, add 20wt% barium hydroxide solution 80-100Kg, filter, collect filter residue and filtrate respectively.

Filter residue with in 10L water, heated and stirred 20min, at suction filtration, filtrate and front filtrate merge, and filter residue leaches 20min putting in 10L water, then suction filtration, merge three filtrates, be heated to 80-90 DEG C, regulate pH6-7 with 10wt% sodium carbonate, filtered while hot, removing precipitation, adds 8Kg solid chlorine barium, be cooled to 5-10 DEG C, suction filtration, precipitation cold water, washing secondary, removing Cl-, 80-100 DEG C of drying in vacuum drying oven.

Claims (2)

1. a preparation method for barium diphenylaminesulfonate, is characterized in that: step is as follows:

(1) add 5Kg pentanoic in a reservoir, add the 4L vitriol oil, add whipping appts and reliever, be warming up to 155-160 DEG C, start reliever under stirring, decompression steams water, inspection sulfonation degree, if sulfonation is incomplete, increases decompression dynamics, steams water more fast;

(2) after sulfonation completes, add 1-2 times of volume water to be hydrolyzed reaction, at 120-125 DEG C of insulation 20-30 minute, add stirring, then pour into rapidly in the boiling water of 10-15 times of volume, add the 50wt% hydrated barta hot solution of 5-7 times of weight, insulation precipitation 1-2 hour, filter, collect filter residue and filtrate respectively;

(3) filter residue 2-3 times of volume hot-water soak 10min, then suction filtration, filtrate and front filtrate merge, and precipitation can discard, and filtrate is heated to 60-90 DEG C, adjust pH6-7 with 10wt% sodium carbonate solution; Heat filter, removing precipitation, adds the solid chlorine barium of 1-2 times of weight, stirs, is cooled to 5-20 DEG C, and have precipitation to generate, suction filtration precipitates, and washes away most of Cl with cold water ^-, after vacuum drying oven 80-100 DEG C drying, namely obtain product, measure its sensitivity, if defective, recrystallization is purified once.

2. the preparation method of barium diphenylaminesulfonate according to claim 1, is characterized in that: described pentanoic: vitriol oil weight ratio=1:1.15-2.0.