WO1998038127A1

WO1998038127A1 - Method for preparing phosphoric acid

Info

Publication number: WO1998038127A1
Application number: PCT/PL1998/000003
Authority: WO
Inventors: Bronis$m(D)aw TREFLER; Stanis$m(D)aw FOLEK; Kazimierz $m(C)ACH; Jeremi MARSZA$m(C)EK; Piotr Masztalerz; Jan Sosnowski; Jerzy Sowa; Zbigniew Tomaszewski; Andrzej Wysocki
Original assignee: Zak$m(c)ady Chemiczne 'police' Sa; Instytut Chemii Nieorganicznej
Current assignee: Zak$m(c)ady Chemiczne 'police' Sa; Instytut Chemii Nieorganicznej
Priority date: 1997-02-26
Filing date: 1998-01-30
Publication date: 1998-09-03
Anticipated expiration: 1999-08-26
Also published as: AU733232B2; DZ2434A1; PL184613B1; EP0966399A1; TNSN98032A1; US6365117B1; EG21405A; MA24486A1; IL131072A0; PL318706A1; TR199902020T2; CA2279953A1; JP2001513742A; AU5580098A; JO2005B1

Abstract

A method for preparing phosphoric acid from calcium phosphate ores, particularly ores highly contaminated with organic compounds, by decomposing the ore with sulphuric acid, wherein according to the invention the process of decomposition of calcium phosphate ores with sulphuric acid and circulating phosphoric acid is carried out in oxidizing conditions provided by a constant supply of ozone to the reaction slurry, preferably to the zone of commencing decomposition of the phosphate ores.

Description

Method for preparing phosphoric acid

The present invention relates to a method for preparing phosphoric acid by a wet method, so called extraction phosphoric acid, from calcium phosphate ores, e.g. phosphorites and apatites and sulphuric acid.

In processes for production of extraction phosphoric acid mainly ground mineral phosphorites or phosphorites enhanced by concentration processes are used. These contain generally fluoroapatite, frequently supplemented with small quantities of mixed apatites and, depending on the origin, various mineral contaminants such as quartz, calcite, dolomite, loamy matter and variously mineralized organic compounds and/or organic compounds introduced in the course of concentration.

From the chemical point of view natural calcium fluorophosphates are always accompanied by great number of various salts of magnesium, aluminium, iron and other cations including rare earth and radioactive elements. Organic contaminants of phosphorites comprise mainly humus and bituminous compounds with a small concentrations of sulphur (II), phosphorus (III) and nitrogen compounds.

In the process for production of extraction phosphoric acid the basic reactions of decomposition of apatite with sulphuric acid are accompanied by a number of various simultaneous side reactions of said contaminants. These reactions influence greatly the quality of phosphoric acid and the course and yield of the process for production of the same.

Organic contaminants of phosphate ores exert a particularly adverse effect on the process for production of phospnoric acid. Already at the extraction stage they are adsorbed on the surfaces of gypsum crystallisation, block active sites of crystals and limit capabilities of their growth. In consequence of this suspensions hard to filter appear having sticky structure of a filtered precipitate and high content of residual phosphoric acid hard to wash out.

The substantial part of organic contaminants is dissolved m resulting phosphoric acid giving it a typical dark-brown colour and enlarging its viscosity and surface tension. Gaseous reaction products, generally carbon dioxide, under this conditions bring about an abundant and stable foam which lowers the rate of extraction and mass yield of the reactor.

Some known and most frequently used mechanical and chemical methods for quenching foam are not always useful and frequently ameliorate the arduousness of the occurrence to a small degree only.

At high temperatures of reaction with phosphoric acid and sulphuric acid the organic compounds contained m some phosphorites liberate to the flue gases vapours of both saturated and unsaturated fatty acids, various organic amines, sulphides and phosphmes distinguishing with their strong, repulsive odour. Having been vented with flue gases to the atmosphere, the compounds can be detected even m trace amounts m the distance of tens of kilometres from the phosphoric acid production facility. Attempts to deodorise the vented gases by known methods, e.g. thermal and catalytic oxidation, adsorption on surface active materials, or destruction m bio-reactors failed to achieve success, though the methods are successfully utilised m another brancnes of industry, e.g. heavy chemical synthesis, tobacco industry, food industry etc.

According to the current state of knowledge the only known efficient method of making phosphorites witn nigh content of organic contaminants suitable for the process for production of extraction phosphoric acid is to precalcme phosphorite m oxidizing conditions at temperatures of alkaline earth carbonates decomposition. However, the method is energy-consuming and applied m special cases, e.g. to produce special extraction phosphoric acid completely devoid of organic contaminants for further purification by solvent extraction. Most frequently such phosphorites are not processed, though they are cheap and readily available, and raw materials more expensive, but less troublesome m processing are used.

Therefore, the object of the present invention is to make independent the process for preparing phosphoric acid by a "wet" method independence of the type and kind of calcium phosphate ore, and particularly of the type and amount of organic contaminants contained therein, at eliminating the emission of offensive odours, at the distinct reduction of reaction pulp foaming and at improving the filtrating properties of resulting phosphogypsum.

This objectis achieved through a method for preparing phosphoric acid from calcium phosphate ores, especially the ores highly contaminated with organic compounds, by decomposing the ore with sulphuric acid, wherein according to the invention the process of decomposition of the calcium phosphate ores with sulphuric acid and circulating phosphoric acid is carried out m oxidizing conditions by a constant supply of ozone to the reaction slurry, preferaoly to the zone of commencing decomposition of the phospnate ores .

The experiments have shown that organic compounds introduced with phosphorites to the extraction process change their pnysicochemical properties under the influence of strong oxidizers, such as peroxide compounds, or particularly fast and efficiently under the influence of gaseous ozone, introduced to the reaction. The oxidation products are almost completely insoluble m phosphoric acid, thus explaining the disappearance of adverse effects of organic contaminants. In particular the viscosity and surface tension are significantly reduced giving directly rise to over 60-ε vanishing of foaming of phosphorites reacting with acid, and vent gases emerging from quickly vanishing foam are completely devoid of the original repulsive odour. At the same time the presence of ozone causes calcium sulphate dihydrate to precipitate as uniform and well shaped crystals. The slurries thus formed are easy to filtrate, and resulting filter cakes are easily wasned off of the acid. The filtrate acid contains emulsified insoluble organic compounds which coagulate readily and sediment with the secondary precipitate. The settled acid loses its typical brownish colour getting clear pale green or olive-green tinge.

One of the advantage of the invention is the fact that it is reliable and effective for various calcium phosphate ores despite of their origin, type and kind, and particularly despite of the type and concentration of organic contaminants.

The additional advantage is the simplicity of the inventive method wnich enables using it without any essential modifications of techniques for preparing extraction phosphoric acid and any structural changes m tne apparatus on the production plant except for adding an ozone generator and the means for feeding ozone to the reactor.

The method is illustrated below oy the way of example.

Example

The Example illustrates the course of the process m a single multi-section model reactor provided with a central two-level blade agitator for test research of usefulness of calcium phosphate ores for preparing extraction phosphoric acid according to a scheme depicted on the enclosed Figure.

To the central cnamber 525 kg/h of circulating slurry at 80°C containing 34% of crystalline CaSθ4x2H2θ m phosphoric acid at a concentration of 301 P2°5 and 10 kg/h of phosphorite containing 29.5% P2O5, 32% Ca, 2.8% F, 0.54% organic compounds expressed as elemental carbon is introduced with continuous stirring, and 0.6 g/h ozone as a 16% (w/w) mixture with pure oxygen or a 4% (w/w) mixture with air is constantly charged. Ozone is introduced ust below the level of upper blades of the agitator through a diffuser to diffuse the gas m the highest degree throughout the reaction slurry. The temperature m the reactor is kept at 82±2°C. The slurry is then supplemented m the calcium sulphate crystallization zone with 8.8 kg/h sulphuric acid at a concentration of 95% diluted previously to 56% with a mixed solution of a phosphoric acid prefiltrate and gypsum washings at a rate of 6.1 kg/h.

After averaging the chemical composition of the slurry in the homogenization zone 90% of the mass is directed to an adiabatic evaporator to concentrate it and subsequently recirculate to the zone of the initial ore decomposition. The rest of the slurry is directed to stages of maturing and subsequent filtration. The process produces about 9.4 kg/h of extraction phosphoric acid at a concentration of 30* P2°5_> which after 24 h maturing becomes a clear solution of pale green or olive-green colour containing about 0.03 of organic matter expressed as carbon. The filtered phospnogypsum at a rate of

29.6 kg/h comprising 13.5% P2O5 is washed with 21.6 kg/h water yielding 22.7 kg of washings containing 17% P2O5 and

21.7 kg/h of washed phosphogypsu at a moisture level of 25~ and containing at average total 0.8 P2O5.

Claims

1. A method for preparing phosphoric acid from calcium phosphate ores, particularly ores highly contaminated with organic compounds, by decomposing the ore with sulphuric acid, characterized m that the process cf decomposition of calcium phosphate ores with sulphuric acid and circulating phosphoric acid is carried out m oxidizing conditions provided by a constant supply of ozone to the reaction slurry.

2. The method according to claim 1, characterized m that ozone is supplied to the zone of commencing decomposition of the phosphate ores.