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CHE4036Z (DESIGN PROJECT) 2011 Design Brief

Introduction You are required to design a process for the treatment of a waste water stream contaminated with sulphuric acid, Ti0 2 and Fe 2+ (aq) . This stream is a by-product of an existing process which extracts titanium from its ore (hereafter referred to as the parent process). The objective is to filter out and remove the Ti0 2 (for recycle to the parent process), react the H 2 SO 4 with CaCO 3 (limestone) to produce CaSO 4 (gypsum) and oxidize the Fe 2+ (aq) to insoluble Fe 3+ , which results in a marketable product (red gypsum) that is used in the manufacture of cement. A maximum of 5 wt% CaCO 3 can be tolerated in the gypsum product. Any residual water must be discharged to a local river, and must therefore contain less than 2050 mg/l of SO 4 2- and 150 mg/l of Fe 2+ . The plant must produce 60,000 tons per year of dry red gypsum (CaSO 4 . 2H 2 O (S) + Fe(OH) 3(s) ). The final free water content of the gypsum must be < 15 wt% before drying and <5 wt% after drying. The process can be continuous, batch or semi-batch and should operate for 8000 hours / year. Many of the streams in this process involve slurries, which must be continuously agitated to avoid settling and possible blockages.

Process Overview Figure 1 shows a process overview, divided into 6 areas.

Area 1: Acid/Lime Mixing

The acidic waste stream is received daily by road tanker with the following composition:

H 2 SO 4 18.90 wt% FeSO 4 6.48 wt%

TiO 2 4.00

wt% (mean particle diameter 5 μm)

The first operation is a filtration process to remove the TiO 2 present as suspended solids. Once recovered, this material is re-cycled back to the parent process. The company operating the parent process collects the TiO 2 , and in return pays nothing for it. A mixing system then combines the filtered waste stream with a CaCO 3 slurry stream from Area 2. The Area 1 engineer

will need to decide how to control the relative feeds of these two materials into the mixing unit.

Area 2: Lime Preparation

CaCO 3 (limestone) is to be received via lorry from a local quarry. The mean size of the rock pieces received is 4 cm, which must be reduced significantly in a ball mill, in order to speed up subsequent reactions in this process. The discharge from the mill is fed to a hydrocyclone where larger particles are recycled to the mill and smaller particles, in the form of a slurry, are fed into area 1. The mean particle size of this slurry must be optimized - smaller particles reduce the efficiency of mill / hydrocylone circuit, but give faster reaction rates later in the process. Another key decision is the quantity of water fed into the mill – too little and the resulting slurry cannot be pumped easily, too much and the subsequent reactor volumes will be excessively large.

Section 3: Initial Reaction Stage

The mixture of acid solution and limestone slurry is fed to a series of stirred reactors (CSTRs). The reaction that occurs is:

H 2 SO 4 + CaCO 3 +2.H 2 OCaSO 4 .2H 2 O + CO 2 + H 2 O Note that the CO 2 will be particularly pure (except during start-up) and hence of commercial value – it should be compressed (and possibly dried) for storage and subsequent sale. This section of the plant is likely to be continuous.

Section 4: Maturation Stage

The slurry is then fed to a maturation stage where O 2 is bubbled through it. The following two reactions occur:

4 Fe 2+ + O 2 + 4 H + 4 Fe 3+ + 2 H 2 O Fe 3+ + 3 H 2 O Fe(OH) 3 + 3 H + The insoluble Fe(OH) 3 precipitates onto the surface of the gypsum crystals, giving them a reddish tinge – hence the name ‘red gypsum’. Note that additional H 2 SO 4 is formed in the 2 nd reaction, which must also be converted to gypsum. The O 2 could perhaps be continuously re-cycled with a make-up inlet and a purge.

Section 5: Product Filtration

The gypsum slurry is then fed to a batch filter press process. The filter presses are equipped with a) pressurised membranes that can squeeze the product filter cake and so remove additional water b) an air-blow system to further reduce the moisture content to ~15 wt% The separated water is fed to a settler unit to remove any remaining solids, and can then be recycled to feed Area 2.

Section 6: Product Drying

The filter cake is fed into a drying unit to further reduce its moisture content to < 5 wt %. Several

equipment options are available for this unit operation. The final red gypsum product is stored and then shipped out once a week by truck.

Other Requirements

  • 1. The plant should be designed to allow for a future expansion to twice its capacity. This will primarily affect the plant layout.

  • 2. The production of CO 2 in this process is environmentally unattractive. In order to secure the support of investors, local authorities and the public, the plant should be designed so that it can be converted at some future date to use CaO instead of CaCO 3 . Unfortunately, in air CaO rapidly converts to CaCO 3 , and this should be taken into consideration.

Location The plant will be constructed at a green-field site with road and rail connections, 10 km from Pofadder, Northern Cape, South Africa. There is no steam available on site, but service water is available at 5 barg / 20 ºC, and fuel oil can be delivered.

Financial Data Costs (ex. VAT):

Acid Waste


1.60 / m 3

O 2

ZAR 1000 / tonne

CaCO 3

(4 cm pieces)


320 / tonne


(4 cm pieces)


840 / tonne

Residual water to river


0 / m 3

Solid effluent disposal


30 / tonne



1.1 / kWh

Service Water


13 / m 3

Fuel oil Selling prices (ex. VAT):

ZAR 9200 / tonne

Red gypsum (15 wt % H 2 O)


560 / tonne



5 wt % H 2 O)


700 / tonne

CO 2

(30 barg)


800 / tone

ZAR 4.5 / m 3 if SO 4 2- > 2050 or Fe 2+ > 150 mg/l

}if Fe 2+ (aq) < 90 mg/l, increase by 50%