GB1560524A - Method of preparing sulphur dioxide - Google Patents

Method of preparing sulphur dioxide Download PDF

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Publication number
GB1560524A
GB1560524A GB4608177A GB4608177A GB1560524A GB 1560524 A GB1560524 A GB 1560524A GB 4608177 A GB4608177 A GB 4608177A GB 4608177 A GB4608177 A GB 4608177A GB 1560524 A GB1560524 A GB 1560524A
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sulphur
oxygen
fluidized bed
per cent
vapour
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GB4608177A
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LE TEKNOLOG I IM LENSOVETA
NII UDOBRENIAM I INSEKTOFUNG I
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LE TEKNOLOG I IM LENSOVETA
NII UDOBRENIAM I INSEKTOFUNG I
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00Sulfur; Compounds thereof
    • C01B17/48Sulfur dioxide; Sulfurous acid
    • C01B17/50Preparation of sulfur dioxide
    • C01B17/54Preparation of sulfur dioxide by burning elemental sulfur

Description

METHOD OF PREPARING SULPHUR DIOXIDE (71) We, LENINGRADSKY TEKHNOLOG ICHESKY INSTITUT IMENI LENSOVETA, of Moskovsky prospekt 26, Leningrad, and NAucHNo-IssLEDovATELsKY INSTITUT PO UDOBRENIAM I INSEKTOFUNGITSIDAM IMENI PROFESSORA Ja. V. Samoilova, of Leninsky prospekt 55, Moscow, both Union of Soviet Socialist Republics, both Corporations organised and existing under the laws of the Union of Soviet Socialist Republics, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement.

This invention relates to a method of preparing sulphur dioxide which will find use in the manufacture of sulphuric acid and in the pulp-and paper industry.

The present invention provides a method of preparing sulphur dioxide comprising melting sulphur, bubbling oxygen through the molten sulphur to evaporate the sulphur, allowing the formed sulphur vapour to pass into a fluidized bed of an inert material, oxidizing the sulphur vapour in the fluidized bed by means of a separate supply of oxygen fed to the fluidized bed, and subsequently isolating the end product.

The method according to the invention makes it possible to burn sulphur directly in a stream of oxygen, which intensifies the process of preparing sulphur dioxide.

Sulphur is preferably evaporated by bubbling oxygen through molten sulphur at a temperature at which the sulphur boils, which ensures maximum evaporation of sulphur.

The sulphur is preferably evaporated and the sulphur vapour oxidized under a pressure of from 1 to 35 atmospheres.

Quartz sand, silica gel or aluminosilicate is preferably used as the inert material of the fluidized bed.

The invention will be further described, by way of example only, with reference to the accompanying drawing, which is a schematic view, partly in section, of an apparatus for carrying out the method according to the invention of producing sulphur dioxide.

Referring to the drawing, crushed sulphur is melted in a chamber 1, heated by steam through coils 2, or by any other suitable method. Molten sulphur is then purified by passing through a filter chamber 3 which also contains heating coils 2. The molten and purified sulphur, at a temperature of 140-1500C, is delivered by a pump 4 into a bubbling chamber 5 of a furnace, where oxygen is sparged through the molten bed 7 of sulphur by a bubbler 6.

The oxygen delivery rate is calculated with respect to the heat and material balance, and depends on the process parameters. Because of the chain character of the burning process, sulphur vapour burns in oxygen in tenths of a second. The temperature inside a bubble rises suddenly and attains a level close to the theoretical temperature of adiabatic burning of sulphur in oxygen (about 3000-3500"C).

As the gas bubble rises through the molten sulphur, it exchanges its heat with the molten bed 7, the heat-exchange process being completed at a depth of 1-1.5 m from the melt surface to the bubbler (experimental data). During the process, the gas bubbles do not come into direct contact with the elements of the apparatus, and the walls of the reaction chamber are not heated above the temperature of the melt.

The composition of the vapour-gas mixture, as it issues from the bubbling chamber 5, is determined by the process parameters, such as pressure, temperature, and heat loss. In the method described, the heat of the reaction in the bubbling zone of the furnace is consumed to evaporate sulphur, and to heat the melt to the working temperature.

The composition of the mixture can be regulated by withdrawing part of the heat using special heat-exchangers 8 located in the bubbling bed.

Sulphur vapour and part of the sulphur dioxide are passed through a gas distributing grating 9 into a fluidized bed 10 of inert material. Secondary oxygen is delivered through a bubbler 11 in a small excess (1-1.5 per cent with respect to stoichiometric) if 100 per cent SO2 is required.

By varying the amount of excess oxygen, the required concentrations of SO2 in the gas are obtained. Heat-exchangers 12 serve to withdraw heat from the fluidized bed zone. The high values of the heat transfer coefficient in the fluidized bed make it possible to maintain the temperature in the bed at 600-7000C. Common lining and construction materials can thus be used in the manufacture of the apparatus.

The capacity of the apparatus for preparing sulphur dioxide under pressure decreases with increased pressure. The specific capacity of the furnace for the manufacture of sulphur dioxide by the method described is about 2-3 times higher than that of apparatus used in previously known methods.

Carrying out the method according to the invention of preparing sulphur dioxide under pressure increases the productivity to 2000 kg per square metre of the bed surface per hour the pressure being 10-35 atm, and the intensity being 3000-3500 kg/sq. m x hr under a pressure of 1-10 atm.

The method described has the following advantages: 1. The concentration of SO2 in the obtained gas can be increased to 100 per cent.

2. The concentration of oxygen in the blowing gas can be as high as 100 per cent by vol.

3. Bubbling of oxygen through molten sulphur at its boiling point, or at a lower temperature markedly increases the evaporation surface so as to intensify the process by 1.5-3 times as compared with previously known methods.

4. The temperature of the medium at the bubbling stage does not exceed 700-800"C, which makes it possible to use common (nonrefractory) construction materials.

5. Burning of sulphur in a fluidized bed of an inert material makes it possible to remove the heat, liberated during oxidation of sulphur by oxygen, directly from the reaction zone.

6. Oxidation of sulphur in the form of vapour in a fluidized bed of an inert material, and intense mixing of the vapour with oxygen, make it possible to complete the process in the bed, the temperature in the zone above the bed not exceeding the temperature of the bed.

7. The intensity of sulphur burning in the form of vapour in a fluidized bed of an inert material is increased by 2-3 times as compared with previously known methods.

8. The method described makes it possible to obtain sulphur dioxide gas having a concentration of 100 per cent from sulphur and oxygen under a pressure of up to 35 atm.

The invention will be further described with reference to the following illustrative Examples.

EXAMPLES Crushed sulphur containing up to 5 per cent by weight of admixtures was delivered into a melting zone by a screw feeder at a rate of 7740 kg/hr. As sulphur melted, it was purified, and passed at a temperature of 140-150 C into a bubbling chamber of a furnace. The crosssectional area of the bubbling chamber was about 3 sq.m, and the diameter thereof was 2 metres. The height of the sulphur melt was maintained at 1 metre (under stationary conditions). The bubbling chamber was a separate apparatus, 3.5 m high. The height of the separation space above the melt was 0.8 m, and the height of the settling zone was 1.2 m. The consumption rate of purified sulphur was 7370 kg/hr. Technical oxygen, containing up to 2 per cent by volume of inert gas, was used in the manufacture of sulphur dioxide.

The process was effected under a pressure of 10 atm and at a temperature of the melt equal to the boiling point of sulphur at a given pressure (646.l0C). This temperature was maintained in the bubbling chamber by the heat liberated in the oxidation reaction of part of the sulphur with oxygen as it was bubbled through the molten sulphur. The quantity of oxygen at a temperature of 15-20"C used for bubbling, under stabilized process conditions, was 626.5 kg/hr or 438.5 cu.m/hr (at STP). The quantity of inert gas that was bubbled together with oxygen was 28.9 kg/hr or 23.1 cu.m/hr (at STP).

During the starting period, oxygen was heatedto a temperature of 350-4000C. As the process conditions became stabilized, the oxygen reacted in the melt with the sulphur vapour. The reaction inside the gas bubbles was completed. A vapourgas mixture was formed as a result in the space above the molten sulphur, the mixture consisting of sulphur vapour (6743 kg/hr or 4720 cu.m/hr, at STP), sulphur dioxide (1253 kg/hr or 433.5 cu.m/hr, at STP), and inert gases (28.9 kg/hr or 23.1 cu.m/hr, at STP). The output capacity of the bubbling chamber was 2500 kg/hr x sq.m.

The vapour-gas mixture was delivered through a gas distributor into the chamber having an inner cross-sectional diameter of 1.7 m and a height of 3.4 m. The chamber was an apparatus where crushed quartz, having particles of size 1.5 mm, was fluidized. The height of the fluidized bed was Ho = 1.2, which ensured complete combustion of sulphur vapour in an oxygen stream at a temperature of 650"C. Excess heat of the reaction was withdrawn by heat-exchangers located in the fluidized bed. The temperature of the gas at the exit from the apparatus had the same value.

The quantity of oxygen to be delivered into the fluidized bed was calculated on the assumption that the obtained sulphur dioxide would be further oxidized to sulphur trioxide. For this reason, the total required quantity of oxygen (for the summary reaction) was delivered into the furnace. Since part of the oxygen was bubbled, the total required quantity of oxygen was 11,274 kg/hr, the excess factor being X = 0.02. Thus 7453.4 cu.mlhr (at STP) of oxygen were delivered into the fluidized bed of an inert material through a special device.

The composition of the gas which issued from the furnace was as follows: oxygen 32.9 per cent by volume, which is equivalent to 3905 kglhr or 2733 cu.m/hr (at STP); sulphur dioxide 62.1 per cent by volume, which is equivalent to 14,740 kg/hr or 5159 cu.m/hr (at STP); and inert gases 5 per cent by volume, which is equivalent to 518 kg/hr or 415 cu.m/hr (at STP).

The production capacity of the furnace, with respect to sulphur dioxide gas having the specified composition, was 8300 cu.m/hr (at STP).

EXAMPLE 2 The process is carried out as described in Example 1, except that the pressure was 15 atm, and the temperature of the molten sulphur was maintained at 650"C, which was below the boiling point of sulphur at this pressure. Liquid sulphur (20412 kg/hr) was evaporated in the bubbling chamber by passing 1113.9 kglhr of technical oxygen containing 15 per cent by weight of inert gas admixtures.

As a result, 19,347.3 kg/hr of sulphur vapour, 2130 kg/hr of sulphur dioxide, and 49 kg/hr of nitrogen were obtained in the fluidized bed which has a height of 1.5 m and an inner crosssectional diameter 3.3 m. The vapour-gas mixture was delivered into the fluidized bed of silica gel having particles of size 1.5 mm. The height of the bed was Ho = 1.2 m, the diameter of the apparatus in the working zone was 1.6 m, and the gas velocity, in the working conditions, was wp = 0.75 m/second. Oxygen was delivered into the fluidized bed in the quantity required for complete oxidation of sulphur vapour and sulphur dioxide to sulphur trioxide. Taking into account the excess ratio factor X = 0.02, this quantity was 30,166 kg/hr, or 21,116 cu.m/hr (at STP). Technical oxygen containing 5 per cent by volume of inert gas was used in the process.The temperature in the fluidized bed was maintained at 650"C. The following products were obtained at the exit from the furnace: sulphur dioxide 40,824 kg/hr or 14,290 cu.m/hr (at STP); oxygen 10,819 kglhr or 7571 cu.m/hr (at STP); nitrogen 1437 kglhr or 1149 cu.m/hr (at STP) The composition of sulphurous acid gas was: SO2 62.1 per cent by volume; 2 32.9 per cent by volume; N2 5 per cent by volume.

EXAMPLE 3 The process was carried out as described in Example 1 except that the pressure was 25 atm, and the temperature of the molten sulphur in the bubbling chamber was 6500C, which was below the boiling point of sulphur at this pressure. Excess heat was withdrawn by heatexchangers that were located directly in the molten sulphur bed. Liquid sulphur having a temperature of 140-l500C was delivered into the bubbling chamber at a rate of 30,234 kg/hr.

The height of the molten sulphur bed was 1.5 metre. The diameter of the apparatus was 3 metres, and its height was 16 metres. Technical oxygen was delivered into the apparatus under a pressure of 25 atm at a rate of 4559.9 kg/hr.

The amount of delivered nitrogen was 20 kglhr.

The gaseous mixture discharged from the bubbling chamber consisted of sulphur dioxide (9120 kglhr, which was 18.4 per cent by volume) sulphur vapour (25,675 kglhr, 81.2 per cent by volume) and inert gases (20 kg/hr, 0.42 per cent by volume). The mixture was delivered into the fluidized bed of silica gel (particle size, 1.5 mm).

Technical oxygen containing nitrogen (183.5 kg/hr) was delivered into the fluidized bed at a rate of 41, 699 kg/hr. Sulphur vapour was completely oxidized in the fluidized bed at a temperature of 650 C, which was maintained at this level by withdrawing excess heat from the fluidized bed. The resultant gas consisted of sulphur dioxide, 64.95 per cent by volume (60,468.6 kg/hr); oxygen, 34.55 per cent by volume (16,024 kg/hr): and inert gases, 0.5 per cent by volume (203.5 kg/hr).

EXAMPLE 4 The process was carried out under a pressure of up to 35 atm on a pilot plant. From a melting chamber, having a capacity of one cubic metre, sulphur was loaded periodically into a bubbling chamber in a quantity of 0.017 cu.m. The diameter of the chamber was 0.3 m, and the bed height was 1 m. The total delivery of oxygen was 60 cu.m/hr (STP). The quantity of oxygen spent for bubbling was 20 per cent of the total quan tity of oxygen. The production capacity of the evaporator was 130 kg/hr, the intensity of evaporation being 2000 kg per square metre of the surface per hour. The inert material used in the fluidized bed was specially treated aluminosilicate catalyst having particles of size 1-1.5 mm.

The height of the bed was Ho = 0.5 m. The temperature in the fluidized bed was maintained at 600-6150C. The composition of the gas discharged from the furnace was: SO2 48-50 per cent by volume 2 30-40 per cent by volume SO3 1.8-2 per cent by volume inert gases to make 100 per cent.

EXAMPLE 5 The process was carried out on a pilot plant under atmospheric pressure. Pure sulphur was loaded periodically into a cylindrical apparatus, having a diameter of 0.08 m and a height of 1.2 m, and provided with an external electric heater. The cover of the apparatus had two connections, one for a bubble type and the other for taking gas samples. The bubbling height in the cylinder varied from 0.5 to 1 metre. The consumption of oxygen for bubbling varied from 0.5 to 3 cu.m/hr (STP). The analysis of gas taken from the zone above the melt showed a 100 per cent utilization of oxygen, the height of bubbling being 0.5 metre. The temperature of the melt varied from 300 to 4400 C. Electric heating was used to commence the process at small rates of air consumption (0.5-1 cu.m/hr, at STP).The bubbler chamber comprised a cooling coil through which water was passed when sulphur boiled. A vapour-gas mixture was formed in the space above the surface of the molten sulphur. The mixture consisted of sulphur vapour.(l7.0 cu.m/hr, STP) and sulphur dioxide (3 cu.m/hr, STP). The obtained quantity of sulphur vapour was oxidized in a fluidized bed of aluminosilicate (1 mm particles) at a temperature of 650-700"C. The concentration of the obtained sulphur dioxide was 98-99 per cent by volume. The capacity of the apparatus was 3000-3500 kg per sq.m per hour.

WHAT WE CLAIM IS: 1. A method of preparing sulphur dioxide comprising melting sulphur, bubbling oxygen through the molten sulphur to evaporate the sulphur, allowing the formed sulphur vapour to pass into a fluidized bed of an inert material, oxidizing the sulphur vapour in the fluidized bed by means of a separate supply of oxygen fed to the fluidized bed, and subsequently isolating the end product.

2. A method as claimed in Claim 1, in which sulphur is evaporated by bubbling oxygen through molten sulphur at a temperature at which sulphur boils.

3. A method as claimed in Claim 1 or 2, in which the sulphur is evaporated and the sulphur vapour is oxidized, under a pressure of from 1 to 35 atmospheres.

4. A method as claimed in any of Claims 1 to 3, in which quartz sand, silica gel or aluminosilicate is used as the inert material of the fluidized bed.

5. A method of preparing sulphur dioxide substantially as herein described with reference to the accompanying drawing.

6. A method of preparing sulphur dioxide substantially as herein described in any of the foregoing Examples.

7. Sulphur dioxide prepared by the method as claimed in any of Claims I to 6.

**WARNING** end of DESC field may overlap start of CLMS **.

Claims (7)

**WARNING** start of CLMS field may overlap end of DESC **. tity of oxygen. The production capacity of the evaporator was 130 kg/hr, the intensity of evaporation being 2000 kg per square metre of the surface per hour. The inert material used in the fluidized bed was specially treated aluminosilicate catalyst having particles of size 1-1.5 mm. The height of the bed was Ho = 0.5 m. The temperature in the fluidized bed was maintained at 600-6150C. The composition of the gas discharged from the furnace was: SO2 48-50 per cent by volume 2 30-40 per cent by volume SO3 1.8-2 per cent by volume inert gases to make 100 per cent. EXAMPLE 5 The process was carried out on a pilot plant under atmospheric pressure. Pure sulphur was loaded periodically into a cylindrical apparatus, having a diameter of 0.08 m and a height of 1.2 m, and provided with an external electric heater. The cover of the apparatus had two connections, one for a bubble type and the other for taking gas samples. The bubbling height in the cylinder varied from 0.5 to 1 metre. The consumption of oxygen for bubbling varied from 0.5 to 3 cu.m/hr (STP). The analysis of gas taken from the zone above the melt showed a 100 per cent utilization of oxygen, the height of bubbling being 0.5 metre. The temperature of the melt varied from 300 to 4400 C. Electric heating was used to commence the process at small rates of air consumption (0.5-1 cu.m/hr, at STP).The bubbler chamber comprised a cooling coil through which water was passed when sulphur boiled. A vapour-gas mixture was formed in the space above the surface of the molten sulphur. The mixture consisted of sulphur vapour.(l7.0 cu.m/hr, STP) and sulphur dioxide (3 cu.m/hr, STP). The obtained quantity of sulphur vapour was oxidized in a fluidized bed of aluminosilicate (1 mm particles) at a temperature of 650-700"C. The concentration of the obtained sulphur dioxide was 98-99 per cent by volume. The capacity of the apparatus was 3000-3500 kg per sq.m per hour. WHAT WE CLAIM IS:
1. A method of preparing sulphur dioxide comprising melting sulphur, bubbling oxygen through the molten sulphur to evaporate the sulphur, allowing the formed sulphur vapour to pass into a fluidized bed of an inert material, oxidizing the sulphur vapour in the fluidized bed by means of a separate supply of oxygen fed to the fluidized bed, and subsequently isolating the end product.
2. A method as claimed in Claim 1, in which sulphur is evaporated by bubbling oxygen through molten sulphur at a temperature at which sulphur boils.
3. A method as claimed in Claim 1 or 2, in which the sulphur is evaporated and the sulphur vapour is oxidized, under a pressure of from 1 to 35 atmospheres.
4. A method as claimed in any of Claims 1 to 3, in which quartz sand, silica gel or aluminosilicate is used as the inert material of the fluidized bed.
5. A method of preparing sulphur dioxide substantially as herein described with reference to the accompanying drawing.
6. A method of preparing sulphur dioxide substantially as herein described in any of the foregoing Examples.
7. Sulphur dioxide prepared by the method as claimed in any of Claims I to 6.
GB4608177A 1977-11-04 1977-11-04 Method of preparing sulphur dioxide Expired GB1560524A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008034229A1 (en) 2006-09-19 2008-03-27 Bogdan Wojak Gas turbine topping in sulfuric acid manufacture
CN105060257A (en) * 2015-08-18 2015-11-18 山东阳光天润化工设备有限公司 Method for preparing sulfur dioxide by using sulfur paste
US9802153B2 (en) 2016-03-04 2017-10-31 Bogdan Wojak Sulphur-assisted carbon capture and utilization (CCU) methods and systems

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008034229A1 (en) 2006-09-19 2008-03-27 Bogdan Wojak Gas turbine topping in sulfuric acid manufacture
US20090235669A1 (en) * 2006-09-19 2009-09-24 Bogdan Wojak Gas Turbine Topping in Sulfuric Acid Manufacture
CN105060257A (en) * 2015-08-18 2015-11-18 山东阳光天润化工设备有限公司 Method for preparing sulfur dioxide by using sulfur paste
US9802153B2 (en) 2016-03-04 2017-10-31 Bogdan Wojak Sulphur-assisted carbon capture and utilization (CCU) methods and systems

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