AU778267B2

AU778267B2 - Apparatus for analysing reduced inorganic sulfur

Info

Publication number: AU778267B2
Application number: AU32630/00A
Authority: AU
Inventors: Richard Bush; David Murray Mcconchie; Leigh Albert Sullivan
Original assignee: Risatec Pty Ltd
Current assignee: Risatec Pty Ltd
Priority date: 1999-03-22
Filing date: 2000-03-22
Publication date: 2004-11-25
Anticipated expiration: 2020-03-22
Also published as: AU3263000A

Description

WO 00/57174 PCT/AU00/00224 1 APPARATUS FOR ANALYSING REDUCED INORGANIC SULFUR FIELD OF THE INVENTION The present invention relates to an apparatus for the quantitative analysis of reduced inorganic sulfur.

BACKGROUND ART Sulfur is present in the environment in several different forms which may be generally classified as organic and inorganic sulfur. The presence of each form of sulfur has important environmental implications. For example, combustion of both inorganic and organic sulfur produces sulfur dioxide, a greenhouse gas and source of acid rain. Another significant environmental problem is the acid generating potential of a class of inorganic sulfur materials known as reduced inorganic sulfur. These compounds produce acid when materials containing them are mined, excavated or drained, and exposed to atmospheric oxygen.

The term "reduced inorganic sulfur" refers to sulfur in a form that can undergo oxidation and includes mineral disulfides pyrite and chalcopyrite), monosulfides sphalerite, galena and covelline), polysulphides pyrrhotite and bornite), non-stoichoimetric metal sulfides greigite), other sulphides such as chalcocite, sulfites (salts of sulfurous acids) and elemental sulfur. In the present specification and claims the term "reduced inorganic sulfur" will be understood to include any inorganic sulfur compound that can be oxidised.

Further types of naturally occurring inorganic sulfur compounds are the sulfate minerals, such as gypsum, which include sulfur in the oxidized sulfate form. These materials are generally not a source of acid in the environment.

When sulfide bearing material is mined or excavated, oxidation of the reduced inorganic sulfur may occur. The result is acid sulfate soil and acid mine drainage. Acid mine drainage refers to acid water produced by the oxidation of minerals such as pyrite in the presence of water and is one of the major environmental problems facing the mining industry. The oxidation of reduced inorganic sulfur in acid sulfate soils is a global environmental problem affecting more than 12 million hectares of agricultural land worldwide, Substitute Sheet (Rule 26) RO/AU WO 00/57174 PCT/AU00/00224 2 degrading aquatic habitats and corroding concrete and steel infrastructure. It is therefore important for environmental management to be able to measure the amount of reduced inorganic sulfur in a wide range of materials including sediments, soils, mine spoil, sludge, petroleum, mineral ores, fossil fuels and water.

There are several known methods for measuring the sulfur content of a material. Combustion followed by measurement of evolved sulfur oxides is used to measure the total sulfur content the combined inorganic and organic sulfur). Such methods are typically used to measure the sulfur content of coal. Combustion of coal is a major source of sulfur dioxide pollution. However, the combustion method does not distinguish between organic sulfur, reduced inorganic sulfur or mineral sulfates and accordingly cannot be used to accurately quantify the reduced inorganic sulfur in a sample.

The most widely used method for assaying reduced inorganic sulfur is by peroxide oxidation in which the sulfur is oxidised to sulfate. The amount of sulfate liberated by peroxide oxidation is then analysed by conventional wet chemical quantitative analysis. Although this method is the accepted procedure, the present inventors have surprisingly and unexpectedly observed that the method is subject to serious interferences from organic sulfur and sulfate minerals such as gypsum. This interference is particularly important when sediments having low reduced inorganic sulfur are measured. An erroneous estimate of the reduced inorganic sulfur content may lead to the recommendation of costly and/or inappropriate and environmentally damaging management practices.

Other methods for analysing reduced inorganic sulfur, but which are considered to be less accurate than the peroxide oxidation method, include: measuring the total sulfur and soluble sulfur content and estimating the reduced inorganic sulfur content from the difference between the two values. A disadvantage of such differential measurement is that the errors are cumulative.

microscopic examination of a sample, and indirect measurement by estimating the amount of pyritic iron (FeS 2 in a sample. However non-pyritic forms of reduced inorganic sulfur are not measured.

It is therefore an object of the present invention to provide a method and apparatus for measuring the reduced inorganic sulfur content of a sample selectively and accurately.

DISCLOSURE OF THE INVENTION According to a first broad form of the invention there is provided an apparatus for measuring the reduced inorganic sulfur content of a sample, the apparatus having a reaction chamber, means for introducing a selective reducing agent that selectively converts the reduced inorganic sulfur of a sample in the reaction chamber to hydrogen sulfide, and measuring means for measuring the amount of hydrogen sulfide evolved by reaction of the selective reducing agent with the sample, said measuring means analyzing a gas phase containing the evolved hydrogen sulfide to thereby measure the amount of evolved hydrogen sulfide, wherein the measuring means is selected from the group consisting of an IR spectrometer, a gas chromatograph, a mass spectrometer, a turbidimetric analyzer, a gravimetric analyzer and a electrochemical gas analyzer.

The apparatus of the present invention has a reaction chamber for allowing a sample to be tested to be digested by a reducing agent that selectively converts the reduced inorganic sulfur component of a sample to

:H

2 S. The reducing agent should not react with organic sulfur or sulfate i 25 materials to produce H 2 S. Preferred reducing agents include chromous salts, stannous salts and mercurous salts.

An especially preferred reducing agent is acidified chromous chloride. Acidified chromous chloride solutions are typically prepared by passing acidified chromic chloride through a column containing zinc, pre- 30 amalgamated in mercuric nitrate. This process is difficult, slow and requires specialised equipment to minimise atmospheric oxidation of the acidified CrC1 2 Also, acidified CrC1 2 is unstable and can only be stored for a few days.

Thus, it is preferred that chromous chloride is generated in situ in the 3a reaction chamber. Typically, chromium, concentrated HCI, ethanol and distilled water are introduced into the reaction vessel. The chromium is typically in the form of a powder, but may also be added as a pellet or slurry.

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OOO0 O00O *O O WO 00/57174 PCT/AU00/00224 4 The reduction reaction is typically carried out in an inert atmosphere such as nitrogen or argon, but can for short periods of time be conducted in air, such as up to about 20 minutes. Generally, the reaction is carried out at elevated temperatures with or without agitation under reflux conditions. The condenser used in the reflux process may be cooled by any of the known methods including a continuous flow of water or a refrigeration unit. In a particularly preferred embodiment of the invention, the apparatus includes a condenser that is cooled by means of water that is recirculated through a refrigeration unit. This arrangement allows for the apparatus to be in lo the form of a portable unit that is suitable for use in the field.

The apparatus of the invention is typically automated and controlled by a central processor which can control some, or essentially all, of the functions of the apparatus. This allows the apparatus to be operated by non-skilled personnel.

Typically, the amounts of reagents added to the reaction chamber are automatically supplied to the reaction chamber in predetermined quantities in a pre-determined order. Generally, the liquid ingredients are added using a peristaltic pump.

In a further broad form of the present invention there is provided an automated apparatus for measuring the reduced inorganic sulfur content of a sample, the apparatus having a reaction chamber, means for heating the chamber, a condenser, means for introducing a reducing agent into the reaction chamber which converts reduced inorganic sulfur to hydrogen sulfide and measuring means for measuring the amount of hydrogen sulfide evolved.

Typically, the apparatus includes a refrigeration unit for cooling water for the condenser.

The reduced inorganic sulfur composition of the sample may be calculated from the amount of H 2 S evolved by reaction with the reductant.

The H 2 S evolution may be measured by any of the known methods of measuring H 2 S. Such methods include colourimetric, turbidimetric and gravimetric methods. Particularly preferred methods include electrochemical, spectroscopic or chromatographic techniques such as mass spectroscopy, WO 00/57174 PCT/AU00/00224 gas chromatography, UV or IR spectroscopy. A particularly preferred measurement means is an electrochemical gas analyser. Generally, the gas which provides the atmosphere in the reaction chamber also serves as a carrier gas to carry the evolved H 2 S to the measurement means.

The amount of H 2 S evolved may also be measured indirectly.

For example, H 2 S may be oxidised to sulfate or sulfur dioxide. These oxidation products may then be measured by suitable methods including turbidimetric or gravimetric, chromatographic or spectroscopic methods.

The apparatus of the present invention typically includes a means for detecting when the evolution of H 2 S has decreased to a predetermined rate. Typically, this is when H 2 S evolution has substantially ceased. Cessation of H 2 S evolution indicates that the reduction reaction has been completed. When completed, a fresh sample may be analysed. With conventional wet chemical procedures, a sample is allowed to react for a predetermined maximum length of time. The present inventors have observed that the reduction reaction can often take much less time than has traditionally been allowed. Thus, by being able to monitor when the reaction has ceased, sample throughput may be optimised. The apparatus may include an alarm or other signalling device to alert an operator that the reaction has finished.

Alternatively and/or in addition to, the apparatus may have means for automatically disengaging any heating of the reaction chamber and deactivate the condenser on completion of the reduction reaction.

The means for detecting when evolution of H 2 S has ceased may be in addition to, or part of, the H 2 S measuring means. For example a gas sensor or other detection means may be associated with the reaction chamber to detect the H 2 S therein. Gas sensors for detecting the presence of

H

2 S are known.

In the preferred embodiment where the H 2 S measurement means is an electrochemical gas analyser or spectrophotometric analyser, the analyser may be programmed to detect when the rate of H 2 S evolution has decreased.

Preferably the electrochemical gas analyser can measure the 6

H

2 S concentration on a real time basis to allow the rate of H 2 S evolution to be constantly monitored. Typically, the H 2 S evolution data may be represented as a function of cumulative H 2 S concentration v time or absolute H 2

S

concentration v. time.

Different forms of reduced inorganic sulfur react at different rates. Thus, by being able to monitor the rate of H 2 S evolution, information can be obtained as to the relative amounts of different forms of reduced sulfur materials present in the sample.

According to a further broad form of the invention there is provided an apparatus for measuring the amount of reduced inorganic sulfur in a sample, the apparatus having a reaction chamber, a means of introducing a reducing agent that can selectively convert the inorganic reduced sulfur of the sample in the reaction chamber to hydrogen sulfide and means for continually monitoring the amount of hydrogen sulfide evolved.

According to still a further broad form of the invention there is provided a method of measuring the amount of reduced inorganic sulfur in a sample, the method including reacting a sample with a selective reducing agent that selectively converts the reduced inorganic sulfur in the sample to hydrogen sulfide but does not convert organic sulfur or sulfate material to hydrogen sulfide and measuring the hydrogen sulfide evolved by analyzing a gas phase containing the evolved hydrogen sulfide using a measuring means S. selected from an IR spectrometer, a gas chromatograph, a mass spectrometer, a turbidimetric analyzer, a gravimetric analyzer and a electrochemical gas analyzer.

25 The ability to determine the relative amounts of different types of reduced inorganic sulfur is important for environmental management. This enables predictions to be made as to the potential rate of acid generation as :fe: opposed to simply calculating the total acid generating potential of a soil 0 material.

A knowledge of a form of sulfur generally referred to as acid 0 0 volatile inorganic sulfur is of particular importance. Acid volatile sulfur includes monosulfides and non-stoichiometric sulphides such as greigite and mackinawite. In the preferred apparatus in which acidic chromous chloride is generated in situ, the sample can be treated with the concentrated HCI and ethanol only. Neither chromium nor water are added.

Only the acid volatile sulfur fraction will react under these conditions and can thus be selectively analysed. If the total reduced inorganic

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WO 00/57174 PCT/AU00/00224 7 sulfur is required, the same sample can then be treated with the chromous chloride reductant by introducing chromium powder and water into the reaction chamber as described above.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 schematically illustrates a preferred apparatus of the present invention, and Figure 2 illustrates a further preferred apparatus of the present invention.

BEST MODE The apparatus of both Figures 1 and 2 are designed to be fully automated and to be portable to allow onsite use in the field.

The apparatus 11 illustrated in Figure 1 has a removable reaction vessel 12. An operator can place a known volume or mass of a sample to be tested into the reaction vessel. Altemrnatively, the apparatus can include an in-built balance to measure the mass of material in the reaction chamber. The reaction vessel 12 is placed in a heating mantle 13 which is equipped with a magnetic stirrer. In use, the reaction vessel is connected, with an air-tight seal, to inlets 14, 15 and outlet 16. The sealed connection may be provided by any suitable means such as ground glass joints or O ring seals.

The inlet 14 is connected to a chromium powder dispenser 17.

The inlet 15 is connected, with an air-tight seal, to a nitrogen gas source 18 and to acid and water and ethanol reservoirs 19, 20. The reservoirs 19, 21 each have a peristaltic pump 22, 23, 24 for delivering pre-determined amounts of liquids via three way valves to inlet 15. The outlet 16 is connected an insulated condenser 26 which typically has copper pipes surrounding a glass core. Refrigerant is supplied to the condenser 26 from pump 27.

Typically, the apparatus includes a heat exchange apparatus by which heat extracted from the condenser can be used to heat the mantle 13. The upper end of the condenser 26 is connected, via an air-tight seal, to an IR gas analyser 28. A moisture control unit 29 is disposed between condenser and analyser 28.

WO 00/57174 PCT/AU00/00224 8 The apparatus is operated by a central control computer The power source 31 is typically a 12V power supply. However, mains supply of any voltage 110V or 240V), AC or DC, may be used by the incorporation of a suitable adaptor.

To operate the apparatus, an operator places an amount of a sample to be tested in the reaction chamber and places the chamber in the mantle. Prior to analysis, the reservoirs of the chamber are charged with chromium powder, ethanol, water and concentrated HCI respectively. The sample to be tested may be any material containing reduced inorganic sulfur l0 and includes soil, mine spoil, fossil fuels such as coal and oil, sediments, plants and animal materials, water (both naturally occurring and waste), chemical waste and minerals. The samples may be pretreated depending on the nature of the sample. For example the mineral samples may be fine ground prior to analysis.

The apparatus is operated by the computer 30 which can be programmed to fully automate the analysis. If desired manual override capabilities may be included. Under normal operational conditions, all that is required of the operator after placement of the sample in the reaction chamber is to press an "on" switch. This will initiate purging of the system with nitrogen for a pre-determined and monitored flow rate. After a fixed time, pre-determined amounts of chromium powder, water, ethanol and 12N HCI are added to the reaction chamber in turn. The water also serves to flush the HCI from the lines.

The amounts of reagent added will depend on the weight of the sample. For a lg sample, typically about 2.059g chromium powder, ethanol, 28.25mL of 12N HCI and 31.75mL of water are added.

After addition of the reagents, the reaction chamber is heated to boiling with stirring. As H 2 S is evolved it is carried by the nitrogen through the dessicant in the moisture trap 29 to the IR gas analyser 28. The cumulative concentration of the H 2 S gas is calculated by the computer 30 using an algorithm relating H 2 S concentration and gas flow rate. When H 2 S evolution has ceased or fallen below a pre-determined level the computer will terminate WO 00/57174 PCT/AU00/00224 9 the analysis by sequentially disengaging the electrochemical gas analyser, and turning off the heating mantle 13, gas flow and condenser 26. The reaction vessel 12 can then be removed by the operator and cleaned. The apparatus is ready for the next analysis.

The total amount of reduced inorganic sulfur can be read directly from a digital panel or stored digitally. The results may also be presented graphically as either cumulative H 2 S production or real time H 2 S production rates.

The apparatus of Figure 2 is similar to that illustrated in Figure 1 and the same reference numerals refer to the same features.

The apparatus does not include an ethanol reservoir. Ethanol is instead added to reaction vessel 12 together with a sample for analysis. The nitrogen inlet of Figure 1 has been replaced by a pump 35 to introduce air as the carrier gas. The condensor 26 is cooled by water pumped from refrigeration unit 36 via pump 27. The IR analyser has been replaced by an electrochemical gas analyser 37. A H 2 S trap 38 is located between the analyser and vent 39.

The above procedures may be modified to separately analyse the acid volatile sulfur fraction. In this case, the sample and ethanol are placed in the reaction chamber as before, but only HCI (20mL) is added. The heating mantle is not required and remains turned off. If both the acid volatile and total reduced sulfur are required, the first procedure may then be performed on the sample remaining in the reaction chamber. However, it will only be necessary to add 8.25mL of HCI (because 20mL have already been added) plus the chromium powder and water.

It can be seen that the apparatus of the present invention can provide a self contained, portable and automated analyser for reduced inorganic sulfur. At present there is no automated system for quantifying reduced inorganic sulfur. All existing techniques used by industry must be performed by skilled personnel in a well equipped laboratory. Thus, it has hitherto not been possible to analyse reduced inorganic sulfur on site.

Automation of the present apparatus allows onsite analysis. Further, skilled WO 00/57174 PCT/AUOO/00224 laboratory personnel are not required to conduct the analysis.

The present apparatus can be in the form of a completely portable unit which may be operated from a 12V power supply. The present apparatus can also be operated using a mains power supply in the laboratory.

s The use of recirculated chilled water contributes to the ability of the apparatus to be self contained. Such portability and self containment is not practical with conventional wet chemistry techniques.

The ability to constantly monitor H2S evolution and to detect when such evolution ceases also offers significant advantages over wet chemical analytical techniques in which a sample is digested for a set period of time. The present inventors have observed that for some samples, digestion can be completed in about 10 minutes as compared to the standard time of one hour allowed for reaction. Thus by monitoring completion of the reaction, the speed of analysis can be considerably increased.

The present invention also provides a method and apparatus for selectively measuring the reduced inorganic sulfur without interference from organic sulfur and sulfate materials. Still further, the acid volatile sulfur fraction can be selectively measured. Also, by monitoring the rate of hydrogen sulfide evolution, important information can be obtained as to the relative amounts of different types of reduced inorganic sulfur in the sample.

It will be appreciated that various changes and modifications may be made to the embodiments as described and claimed herein without departing from the spirit and scope of the invention.

Claims

1. An apparatus for measuring the reduced inorganic sulfur content of a sample, the apparatus having a reaction chamber, means for introducing a selective reducing agent that selectively converts the reduced inorganic sulfur of a sample in the reaction chamber to hydrogen sulfide, and measuring means for measuring the amount of hydrogen sulfide evolved by reaction of the selective reducing agent with the sample, said measuring means analyzing a gas phase containing the evolved hydrogen sulfide to thereby measure the amount of evolved hydrogen sulfide, wherein the measuring means is selected from the group consisting of an IR spectrometer, a gas chromatograph, a mass spectrometer, a turbidimetric analyzer, a gravimetric analyzer and a electrochemical gas analyzer.

2. Apparatus as claimed in claim 1 further comprising a detector for detecting when evolution of hydrogen sulfide has reduced or ceased.

3. Apparatus as claimed in claim 2 including signaling means for signaling when evolution of hydrogen sulfide has ceased.

4. Apparatus as claimed in claim 2 or claim 3 wherein the measuring means detects when evolution of hydrogen sulfide has reduced or ceased.

5. Apparatus as claimed in any one of the preceding claims further comprising a central control unit for controlling introduction of the reducing agent and any other reagents to the reaction chamber.

6. Apparatus as claimed in claim 5 wherein the central control unit includes calculating means for calculating the amount of reduced inorganic i 25 sulfur in the sample from the measured hydrogen sulfide.

7. Apparatus as claimed in any one of the preceding claims wherein said apparatus is a portable unit.

S8. An apparatus as claimed in any one of the preceding claims further including a reservoir for storing the selective reducing agent or a 30 precursor or precursors thereof.

9. An apparatus as claimed in any one of the preceding claims further including a source of carrier gas in fluid communication with the ireaction chamber for introducing the carrier gas into the reaction chamber and reaction chamber for introducing the carrier gas into the reaction chamber and a fluid passageway for carrying the hydrogen sulfide from the reaction chamber to the measuring means.

An apparatus as claimed in any one of the preceding claims further comprising heating means for heating the reaction chamber.

11. An apparatus as claimed in any one of the preceding claims further comprising a condenser fluidly connected to the reaction chamber and a source of cooling fluid for cooling the condenser.

12. Apparatus as claimed in claim 10 further comprising heater control means for controlling operation of the heating means.

13. Apparatus as claimed in any one of the preceding claims wherein said reducing agent is selected from the group consisting of Cr(ll), Sn(ll), and Hg(l).

14. Apparatus as claimed in claim 13 wherein the reducing agent is chromous chloride.

15. Apparatus as claimed in claim 14 further including means for introducing predetermined amounts of chromium powderand hydrochloric acid into the reaction chamber such that chromous chloride is generated in the reaction chamber.

16. Apparatus as claimed in any one of the preceding claims further comprising a source of acid and means for introducing the acid into the reaction chamber prior to introduction of the reducing agent such that the •g amount of any acid volatile sulfur in the sample can also be measured.

17. Apparatus as claimed in claim 16, further including a source of hydrochloric acid and means for introducing the acid into the reaction 25 chamber prior to introduction of the reducing agent such that the amount of oC. Co any acid volatile sulfur in the sample can also be measured.

18. A method of measuring the amount of reduced inorganic sulfur CC.. in a sample, the method including reacting a sample with a selective reducing agent that selectively converts the reduced inorganic sulfur in the sample to hydrogen sulfide but does not convert organic sulfur or sulfate material to hydrogen sulfide and measuring the hydrogen sulfide evolved by analyzing a •.00gas phase containing the evolved hydrogen sulfide using a measuring means selected from an IR spectrometer, a gas chromatograph, a mass selected from an IR spectrometer, a gas chromatograph, a mass 13 spectrometer, a turbidimetric analyzer, a gravimetric analyzer and a electrochemical gas analyzer.

19. A method as claimed in claim 18 wherein said selective reducing agent is selected from the group consisting of Cr(ll), Sn(ll) and Hg(l) and measuring the hydrogen sulfide evolved.

The method of claim 19 wherein the reducing agent is chromous chloride.

21. The method of claim 20 wherein the chromous chloride is generated in a reaction chamber by introducing predetermined amounts of chromium powder and hydrochloric acid into the reaction chamber.

22. The method of any one of claims 18 to 21 wherein the evolved hydrogen sulfide is measured as a function of time.

23. The method of any one of claims 18 to 22 wherein hydrochloric acid is mixed with the sample prior to mixing of the sample with the selective reducing agent whereby any acid volatile sulfur in the sample is reacted to evolve hydrogen sulfide and measuring the hydrogen sulfide.

24. The method of any one of claims 18 to 23 wherein the evolved hydrogen sulfide is measured in real time and when the measurement detects that evolution of hydrogen sulfide has fallen below a pre-determined minimum, a fresh sample is analyzed.

An apparatus for measuring the reduced inorganic sulfur content of a sample substantially as hereinbefore described with reference to the accompanying drawings. *0

26. A method of measuring the amount of reduced inorganic sulfur 25 in a sample substantially as hereinbefore described with reference to the S* accompanying drawings. Risatec Pty Limited 3 By the patent attorneys for the applicant CULLEN CO. Date: 10 September 2004