Method of aqueous waste halogenides-containing liquors treatment

BACKGROUND OF THE INVENTION The present invention relates to a process for the treatment of aqueous waste liquors containing halides to remove halide ions, in particular lye, which is eliminated during the gasification of coal by a process of ash grinding.

Gas-fired gas-fired gas-fired gas-fired gas-fired gas-fired gas-fired gas-fired gas-fired gas-fired gas-fired gas-fired gas-fired gas-fired gas-fired gas-fired gas-fired gas-fired gas-fired gas-fired gas-fired plants One of the major problems with the waste liquor will be the treatment of the condensed waste liquor from the gas cooling system immediately downstream of the gasifier.

This lye is highly contaminated with ammonia, hydrogen sulfide, other sulfur-containing compounds, halides, cyanides and organic compounds. It represents a totally unacceptable polluting burden for direct discharge into the public sewerage network and free streams.

Conventional methods for treating liquid waste liquor from an ash-disintegrating gasifier, including the removal of phenols, ammonia, biological oxidation, and adsorption on activated carbon, can reduce the content of most pollutants to a level acceptable for discharge into the public sewerage network and free streams. However, even after treatment of this type, the waste liquor can be expected to contain 5,000 to 25,000 mg of chlorides per liter, depending on the coal being treated.

Without substantial dilution, waste liquor with such salt content could currently only be discharged into estuaries or into the sea and it is likely that within a few years further restrictions will be imposed by the authorities.

One conditionally attractive way to get rid of this waste liquor is to reintroduce it into the gasifier. This should result in the gasification of any type of carbon-containing compounds and the conversion of the water present in the waste liquor into an equivalent amount of process steam. Indeed, it has been shown that water can be introduced into the gasifier without any apparent difficulties or damage to the production equipment.

However, a problem which has hitherto rendered the re-introduction of waste liquor into the gasifier impossible is the accumulation of chlorides in the waste liquor circulation system.

Chlorides enter the gasifier as a salt in the coal matrix and pass quantitatively into the waste liquor as ammonium chloride; no chloride passes into the slag and none appears as volatile chlorine compounds in the product gas. Thus, if the condensed waste liquor is recycled to the gasifier so that no waste is generated, the chlorides, otherwise continually removed from the production process through the waste liquor removal system, will accumulate in the waste liquor until they crystallize and clogging of equipment.

The high content of chlorides present will also cause material problems in the gasifier. Until now, there has been no way to remove chlorides from heavily contaminated waste liquor, thus allowing either its reintroduction into the gasifier or its removal into the surface water drain, except

1. treatment according to the usual procedures as described above, followed by dilution with process water to reduce the halide concentration to an acceptable level and then discharging into the watercourse or public sewer, or

12. treatment by conventional processes followed by distillation or reverse osmosis to obtain purified water for return to the manufacturing process and brine which can be evaporated to dryness to yield solid waste.

A number of factors can affect the feasibility of any of these treatments.

For example, in the first alternative, the amount of dilution required to reduce the chloride concentration in the liquor from the gasifier to an acceptable level makes this approach disadvantageous and in any event unlikely that the water authorities would allow water to be used for dilution alone.

The required dilution factor could easily be of the order of 50 times, which would correspond to a requirement of up to 91,000 m³ water per day for one plant with a daily production of 7 million m³ gas. This would not only be very costly, but could also cause difficulties in terms of the amount of water consumed by social consumption.

In a second alternative, the waste liquor is treated according to conventional procedures, which may include various combinations of phenolization, ammonia removal, biological oxidation, moist air oxidation, activated carbon treatment, combustion and reverse osmosis. The resulting pure waste brine is then evaporated to give a solid residue as waste. This process is technically feasible, but expensive, since it requires not only capital investment in complex conventional processing facilities, but also a large amount of energy input that cannot easily be recovered to evaporate the waste brine to dryness.

It has now been found that halides can be removed in a novel and unexpected manner from the waste liquor by contacting the waste liquor in the form of vapors with hot calcium carbonate to obtain a material suitable for re-introduction into the gasifier as reactant.

At a temperature greater than 275 ° C, the ammonium chloride decomposes into ammonia and chlorine. Therefore, most of the chloride is in the gas leaving the gasifier. with a temperature of, for example, about 480 ° C, present as hydrogen chloride. Thus, if a bed of basic material, such as calcium carbonate, is provided between the gasifier and the scrubber-cooler, the chlorides can be removed in solid form as calcium chloride, while the waste liquor condenses virtually chloride-free in a form suitable for re-introduction into the gasifier.

This third possibility, i.e. the removal of chlorides from the gas in the vapor phase, with the subsequent reintroduction of the condensed liquor into the gasifier, is at first sight very attractive. No energy is required, limestone costs for chloride absorption are low and only one reaction vessel is required, so the investment costs are considerably low. Although this is an elegant solution to the problem of getting rid of waste liquor, it was nevertheless expected that dust and tars contained in the gasifier gas would clog the bed of limestone, thereby reducing absorption efficiency and contaminating the resulting calcium chloride, making it difficult to get rid of it.

It has now been found that these problems can be reduced to a minimum by applying a process in which the waste liquor removed after cooling, condensation and separation of the tar, oil and solids contained therein is converted into vapors which are passed through a bed of hot limestone to remove chlorides, then reintroduced into the gasifier as highly polluted water vapor.

When the waste liquor is converted into vapor, i.e. by evaporation, the salts contained therein pass through a temperature range (approximately 100 to 300 ° C) in which they are stable. At temperatures above 300 ° C, the ammonium chloride, which forms the major part of these salts, decomposes rapidly into ammonia and hydrogen chloride. Any other halide reacts similarly. Since the organic compounds are volatile, any solid residue will be minimal if the waste liquor temperature is raised to 300 ° C or higher.

This means that in order to be successful, i.e. to prevent solid salts from settling in the evaporation zone and consequently the subsequent fouling of the limestone bed, the temperature of the waste liquor in the evaporator must be increased from 100 degrees Celsius to 300 ° C as quickly and without contact as possible. vapors formed with any cold surface. Typically, the heating rate in this temperature range will be 50 to 100 ° C per second.

SUMMARY OF THE INVENTION Accordingly, the present invention provides a process for treating halide-containing liquid waste liquors to remove halide ions, wherein the treated waste liquor, for example from coal gasification by ash-grinding, is first removed from tars and heated by evaporation or incineration or heating. the amount of caustic boiling and subsequent superheating of the resulting vapors, thereby converting them into vapors at a temperature of 400 to 500 ° C which are brought into contact with the calcium carbonate in the form of a solid or fluldized bed of limestone maintained at a temperature of 400-500 ° C, characterized in that during heating the temperature rises between 100-300 ° C at a rate of at least 50 degrees Celsius per second.

Although the halide reactions are carried out at a temperature in the range of 400 to 500 ° C, it is necessary to conduct the heating so as to ^ЮС at 300 ° C was the fastest.

Tar-free mixed waste liquors are particularly suitable for processing according to the invention. Table I below provides an analysis of a typical crude gasifier waste liquor useful for synthesis gas.

Table I

Composition of raw waste liquor with gasifier (mg in 1 liter)

<td>free ammonia (as NH3)</td><td> 15 750</td>

<td>bound ammonia (as NH3)</td><td> 3 390</td>

<td>sodium</td><td> 900</td>

<td>potassium</td><td> 400</td>

<td>carbonates (as CO2)</td><td> 27 950</td>

<td>cyanides</td><td> 8</td>

<td>thiocyanates</td><td> 1280</td>

<td>sulphides</td><td> 1779</td>

<td>thiosulfates</td><td> 550</td>

<td>sulfates</td><td> 55'0</td>

<td>chlorides</td><td> 6 200</td>

<td>fluorides</td><td> 120</td>

<td>bromides</td><td> 115</td>

<td>phenols</td><td> 6 903</td>

<td>fatty acids</td><td> 478</td>

<td>other organic substances</td><td> 471</td>

Obviously, after removal of the halides from the waste liquor, the liquor can be reintroduced into the gasifier, since the remaining species will be converted into nitrogen, hydrogen sulfide and carbon oxides.

The bed material in the reactor is calcium carbonate in any suitable form, such as crushed limestone, and the bed itself may be solid or fluidized. It is necessary to provide a device for adding fresh limestone and for removing depleted bed particles, i.e. in the form of calcium chloride.

BRIEF DESCRIPTION OF THE DRAWINGS The invention will now be explained with reference to the accompanying drawings, which show schematically various embodiments of the process for heating the waste liquor to the reaction temperature and subsequent reaction with limestone.

In the first embodiment, schematically shown in Fig. 1, the filtered waste liquor, typically at 25 ° C and pumped under a pressure of 3 MPa, is fed through a supply line

1. The temperature of the waste liquor is raised to 25 ° C at about 90 ° C in the heat exchanger 6 by indirect heat exchange with the combustion gases from the furnace 5; the waste liquor is then sprayed vertically through the injector 2 into the cylindrical vaporizer vessel 3. The injector 2 is inserted sufficiently deep into the cylindrical vaporizer vessel 3 to ensure that the internal wall temperature of the vaporizer vessel is maintained at at least 300 ° C. The outlet of the cylindrical evaporator is maintained at a temperature of 400 ° C to 500 ° C. The hot effluent vapors are then fed directly to the carbonate reactor 4. Typically, the reactor comprises a main section 41 in which the hot vapor from the vaporization vessel comes into contact with the calcium carbonate.

Fresh carbonate is added from hopper 42, while the resulting calcium halides formed by reaction with calcium carbonate are discharged from the bottom of reactor main section 41 to reservoir 43. Both hopper 42 and reservoir 43 can have closures so that the carbonate can and the resulting halides can be removed without reducing the pressure in reactor 4.

In the embodiment shown in Fig. 2, approximately 85% of the waste liquor is converted into polluted vapors by passing the waste liquor supplied by the inlet pipe 1 through a heat exchanger 6 provided in the exhaust chimney 5 of the furnace 5 and into the boiler 31. the boilers 31 are superheated in a heat exchanger 7 to a temperature of approximately 550 degrees Celsius and then introduced into the bottom of the reactor 4. The remaining 15% caustic is also discharged from the boiler 31 to the reactor 4, but at a higher elevation than the superheated steam, and is converted into steam by the superheated steam rising up through the reactor.

In a third embodiment, the waste liquor is evaporated at high pressure in the combustion chamber 5 (Fig. 3) using a burner in which fuel oil is burned in an oxygen stream. The combustion products pass the limestone bed 4 to remove the chlorides and are then re-fed to the gasifier, as shown in FIG.

In a variation of this third embodiment, the combustion chamber and the limestone bed reactor may be combined into a single integral reaction zone. In this variation, it is advantageous to work with a fluidized bed of limestone. In operation, in this variation, the chloride-containing waste liquor will be injected into the hot fluidized bed of limestone together with various fuels, such as tar, diesel, fuel gases, pulverized coal. Inside this fluidized bed combustion furnace, the chlorides will react with the bed material and non-volatile combustion products such as sulfur and other inorganic components will be physically retained on the bed particles.

The invention is illustrated by the following example.

Example

Figure 4 is a schematic representation of a laboratory test apparatus used in testing the method of the invention.

The bed consisted of 5 g of calcium carbonate placed between two plugs of cotton wool. Another silica plug, 50 mm above the bed, formed the evaporation surface for the injection solution. Nitrogen gas flowed down the tube at 4.8 liters per hour.

Two samples of 46 ml and 80 ml of manganese coal gasification effluent, ash ash slagging, were passed through a reactor maintained at 500 ° C for 280 minutes, increasing their temperature in the temperature range of 100 to 300 ° C at 50 ° C. to 100 ° C per second in accordance with the method of the invention. Prior to the start of the experiment, the waste liquor was analyzed by both high pressure liquid chromatography and ion chromatography. After the reaction was completed, the condensate was recovered and analyzed by both methods. The results of both analyzes are shown in Table II.

Table II

<td>Component</td><td>Feeding effluent (mg. I '¹)</td><td>from the first attempt</td><td>Condensate from the second attempt</td>

<td>chlorides</td><td> 6 200</td><td> 9</td><td> 50</td>

<td>fluorides</td><td> 120</td><td> 12</td><td> 47</td>

<td>phosphates</td><td> 1</td><td> 12</td><td> 2</td>

<td>bromides</td><td> 11'5</td><td> 1</td><td> 4,5</td>

<td>nitrates</td><td> 96</td><td> 46</td><td> 0,1</td>

<td>sulfates</td><td> 210</td><td> 47</td><td> 59</td>

<td>thiocyanates</td><td> 1 280</td><td> 297</td><td> 284</td>

<td>thiosulfates</td><td> 5'50</td><td> 296</td><td> 305</td>

<td>phenol</td><td> 3 830</td><td> 3 800</td><td> 3 730</td>

<td>kresoly</td><td> 4 520</td><td> 4 350</td><td> 4 240</td>

<td>xylenes</td><td> 860</td><td> 700</td><td> 650</td>

<td>hydroquinone</td><td> 6</td><td> 3</td><td> 1</td>

<td>resorcin</td><td> 26</td><td> 30</td><td> 20</td>

<td>pyrocatechin</td><td> 50</td><td> 10</td><td> 30</td>

<td>methylresorcines</td><td> 30</td><td> 1</td><td> 1</td>

<td>methylpyrocatechins</td><td> 40</td><td> 1</td><td> 1</td>

<td>5,5-dimethylhydantoin</td><td> 310</td><td> 300</td><td> 270</td>

After the reaction was completed, the calcium carbonate was extracted with water and the extract was analyzed by titration for chloride and ion chromatography for other ions. The results are shown in Table III.

Table III

Component

First attempt absorbed% of bed amount (mg)

Second experiment absorbed% of bed amount (mg) chlorides249 fluorides0,6 phosphates, 2,2 nitrates0,20 sulfates20,6 thiocyanates1,3 thiosulfates0,3

<td> 4,98</td><td> 465</td><td> 9,30</td>

<td> 0,01</td><td> 0,3</td><td> 0,06</td>

<td> 0,04</td><td> 1,4</td><td> 0,03</td>

<td> 0,010</td><td> 0,10</td><td> 0,01</td>

<td> 0,41</td><td> 5,7</td><td> 0,11</td>

<td> 0,03</td><td> 1,3</td><td> 0,03</td>

<td> 0,01</td><td> 0,3</td><td> 0,01</td>

The amount of waste liquor introduced in the first experiment was 46 ml

The amount of chloride introduced in the first experiment

Amount of recovered chloride

Percentage of recovered chloride

Amount of waste liquor introduced in the second experiment

The amount of chloride introduced in the second experiment

Amount of recovered chloride

Percentage of recovered chloride

Average amount of recovered chloride

Bed temperature during both experiments

Nitrogen flow during both experiments

285.2 mg

249 mg

87.3% ml

496 mg

465 mg

93,8 %

90,6 %

500 Deň: 32 ° C

The results clearly show that at least 90% of the chlorides, and possibly up to 99%, are removed by the process according to the invention, when the calculation is based on the reduction of chloride in the waste liquor. Also, the amount of bromides and sulfates is substantially reduced by absorption, while the amount of thiocyanates and thiosulfillates is apparently reduced by thermal decomposition, since neither of these ions is found in the bed after the reaction is complete. The organic compounds are practically unaffected by the reaction, although the thermal degradation of the substituted divalent phenols is partially.

During the experiments, a series of calcium sulfite assays were performed to determine if the carbonate had the ability to absorb hydrogen sulfide. No sulphide was ever detected, despite the fact that sulphides are present in a considerable amount in the waste liquor supplied.

The condensed lye is suitable for use as a reactant in an ash-grinding gasification process.

List of reference marks - supply pipe - injector - cylindrical evaporator vessel - boiler - reactor - main reactor section - hopper - tank -, furnace - heat exchanger - heat exchanger - furnace.

- Silica wadding plug - Silica wadding plug - Calcium carbonate - Flow meter - Injection pump - Condenser - Sample container