EP3506995A1

EP3506995A1 - Method and device for removing organic sulphur compounds from hydrogen-rich gases

Info

Publication number: EP3506995A1
Application number: EP17758506.4A
Authority: EP
Inventors: Michael Rieger; Holger Thielert; Eva KAMP
Original assignee: ThyssenKrupp AG; ThyssenKrupp Industrial Solutions AG
Current assignee: ThyssenKrupp AG; ThyssenKrupp Industrial Solutions AG
Priority date: 2016-09-01
Filing date: 2017-08-25
Publication date: 2019-07-10
Also published as: CN109641176A; DE102016116306A1; UA123236C2; KR102242266B1; KR20190041520A; WO2018041728A1; JP2019529306A

Abstract

The invention relates to a method for separating sulphur from a hydrogen-rich gas containing carbon disulphide compounds and oxygen, in which carbon disulphide compounds are converted into hydrogen sulphide using a catalyst, a noble metal catalyst being used as the catalyst. The use of the noble metal catalyst allows oxygen to be converted into water at the same time as the reduction of the carbon disulphide compounds. Furthermore, the oxygen reduction can provide the energy required to heat the catalyst. The invention also relates to a device for carrying out a corresponding method.

Description

Method and apparatus for removing organic sulfur compounds from hydrogen-rich gases

description

Field of the invention

The invention is in the field of desulfurization of

Industrial gases and in particular relates to a novel process for the removal of carbon sulfides from coke oven gas using a noble metal catalyst and its use.

State of the art

Coke oven gas, often referred to as coking gas, is produced in coking plants during the dry distillation of hard coal. Typically contains

Coke oven gas as main components about 55 wt .-% hydrogen, 25 wt .-% methane, 10 wt .-% nitrogen and 5 wt .-% carbon monoxide. As a result, coke oven gas is basically suitable as a synthesis gas for chemical reactions. Since coal contains a certain amount of sulfur, coking of coal and the like can occur. also carbonyl sulfide and carbon disulfide, which must be removed before further use of coke oven gas, since they act as catalyst poisons in follow-up reactions, for example. Without a removal of

Sulfur compounds would require these catalysts are often cleaned or even replaced, which is directly associated with effort and costs and is additionally undesirable because of the stoppage of the plants.

One way of removing coke oven gas from unwanted carbon sulfides is by subjecting it to catalytic hydrogenation, and the

To convert sulfur compounds into hydrogen sulphide. Although this gas is also undesirable, it can easily be washed out with aqueous alkalis, for example ammonia solutions.

Some processes for the hydrogenation of sulfur compounds are already known from the prior art. For example, in the German Patent Application DE 1545470 AI (Pichler) proposed the carbon sulfides in the coke oven gas in a two-stage process in the presence of cobalt-molybdenum, nickel-molybdenum or nickel-cobalt-molybdenum catalysts

Hydrogenating hydrogen, which can then be separated by conventional methods from the gas mixture. The reaction temperature in the examples is above 550 ° C.

A similar process is also known from the German patent application DE 2647690 AI (Parsons). There is proposed sulfur containing

Hydrogenating carbon compounds in the presence of catalysts based on cobalt, molybdenum, iron, chromium, vanadium, thorium, nickel, tungsten and / or uranium and to remove the resulting hydrogen sulfide in an extraction column using an alkali metal hydroxide solution. As concrete catalysts here the sulfides of the above metals are proposed. A disadvantage, however, is that the catalysts also require a minimum temperature of 260 ° C. in the process specified in DE 2647690 A1 and the hydrogenation must preferably be carried out at significantly higher temperatures, in some cases even above 400 ° C. This is not desirable for reasons of energy consumption; In addition, at these temperatures, there is a change in the composition of the gas, d. H. methanation already takes place.

DE 10 2013 009 885 A1 describes a method for removing

Coke gas sulfur compounds for use in the conversion of sulfur compounds into hydrogen sulfide sulfide cobalt-molybdenum catalysts. These are catalysts which consist predominantly of molybdenum sulfide and contain the cobalt in sulfidic form as a promoter. By using appropriate catalysts was a reduction in the operating temperature in the

Desulfurization to a temperature in the range of 240 ° C to 260 ° C possible, which was associated with the additional advantage of suppressing methane formation.

A problem with desulphurization, especially if it is high

Temperatures are made, industrial gases and in particular

Coke oven gases, which also contain a certain amount of oxygen in addition to sulfur compound. Heating the hydrogen-containing gas in the presence of oxygen can lead to uncontrolled oxyhydrogen gas reactions come through which the reprocessing plant for the coke oven gas can be damaged. The gas to be fed to the desulphurisation should therefore be as free as possible of oxygen before it is fed to the desulphurisation device. The separation of oxygen from gas mixtures such as coke oven gas, however, is technically relatively complicated and thus costly. For this reason, coke oven gas is used today to a significant extent purely thermal (ie by combustion), but due to the sulfur content

Caused schademissionen.

With the catalysts described in DE 10 2013 009 885 AI, the reaction temperature for sulfur compounds could already significantly compared to z. B. the catalysts known from DE 1545470 AI be lowered. However, since the energy required to heat the gas mixtures to the reaction temperature of the catalyst accounts for a significant proportion of the cost of desulfurization, there is a need for catalysts for reducing sulfur compounds from industrial gases operating at low temperatures, such as 200 ° C ° C adequate desulfurization

to ensure.

From DE 10 2011 105 353 Al is a process for the reductive conversion of sulfur-containing hydrocarbons, such as thiophene, CH ₃ SH and 2- and 3-methylthiophene to hydrogen sulfide by means of a

Noble metal catalyst known, this conversion can proceed in the presence of oxygen gas. As a catalyst, for example, a

Platinum / ruthenium catalyst used on a cerium oxide / aluminum oxide / lanthanum oxide support. In this known method, however, contains

hydrogen-rich gas neither COS nor CS ₂ .

In US 2002/0121093 AI a reaction of COS to H ₂ S is described in which catalysts such as Pt on Al ₂ 0 ₃ are used. However, this is not a reduction of

But carbonic acid hydrolysis, in which COS is converted with water to C0 ₂ and H ₂ S. Thus, the

Carbon disulfide COS not reduced, but oxidized. Also, the overall reaction is not a reduction, since this one balanced with respect to the carbon disulfide compound

Total electron balance. From US 4,981,661 A also a method is known in which

Carbon disulfide compounds such as COS and CS ₂ in combination with water to H ₂ S and C0 _{2 are} reacted. However, this method does not reduce a hydrogen-rich gas having a proportion of carbon disulfide compounds and oxygen with a noble metal catalyst. The process is also divided into two steps, with oxygen being separated from the gas mixture in the first step. For example, a Co-Mo catalyst is used for this step. For Pt-based catalysts, it is stated in this document that they have oxidative properties and therefore oxidize H ₂ S, which is present in combination with oxygen, to S0 ₂ . This leads to subsequent reactions with remaining H ₂ S to form sulfur, which can lead to clogging of the device.

JPS 59-232175 A describes the treatment of coke oven gas containing dienes, oxygen, olefins and sulfur compounds as an impurity. Corresponding coke oven gases are reduced in the presence of a palladium-based catalyst on an Al ₂ O _{3 support} to H ₂ S, which can then be absorbed on an adsorbent such as ZnO. COS and CS ₂ are not mentioned in this publication for the sulfur compounds. In the examples, moreover, the composition has an extremely low sulfur content of 0.01% H ₂ S, so it can be assumed that no raw coke oven gas is treated here, but pretreatment steps have taken place, but these are not specified in this document.

The object of the present invention was therefore to propose a method by which the cost of removal of elemental oxygen in industrial gases can be reduced, and at the same time the most quantitative conversion of carbon sulfides present in the gas, and optionally also present organic sulfur compounds (eg. As thiophenes or mercaptans), ensured in hydrogen sulfide, if possible at lower compared to the prior art temperatures. Furthermore, the object of the present invention was to propose a method in which the least possible energy for heating the

Gas mixture must be spent for the desulfurization.

Description of the invention The invention accordingly provides a process for the separation of sulfur from a hydrogen-rich gas containing sulfur-carbon compounds and optionally oxygen, thereby

characterized in that sulfur-carbon compounds are converted with the assistance of a catalyst in hydrogen sulfide, wherein

Catalyst is a noble metal catalyst is used and wherein the

hydrogen-rich gas contains at least one compound selected from the group comprising COS and CS ₂ .

In the context of the present invention, "noble metal" is understood as meaning metals which have a positive normal potential (in aqueous solution at pH 7) to the hydrogen electrode of at least 0.45 V. in the

Preferred noble metals in the context of the present invention are gold, platinum, iridium, palladium, osmium, silver, ruthenium and rhodium, particularly preferred noble metals are palladium, platinum and rhodium, and most preferred are palladium and platinum. The noble metal may consist of one of the metals mentioned or be present as a mixture of several of the metals mentioned.

In the context of the present invention, a "hydrogen-rich gas" is understood as meaning a gas having a minimum content of 20% by volume, preferably at least 40% by volume and particularly preferably at least 45% by volume of hydrogen.

Coke oven gas usually has a hydrogen content of 60-65 vol .-% and thus represents a particularly suitable hydrogen-rich gas in the context of the invention.

By "sulfur-carbon compounds" in the context of the present invention are meant compounds containing sulfur and carbon atoms, but may additionally contain other heteroatoms or hydrogen atoms.

The noble metal catalyst is suitably present in a form bound to a solid support material. As a suitable support materials is mainly alumina, which also in conventional vehicle catalysts as

Carrier material is used, or ceramic into consideration. Suitable aluminas are especially those with high internal surface area.

Alumina carriers of the type mentioned are well known from the prior art. For example, in the European patents EP 1385786 B1 and EP 1385787 B1 (Axens) describes a process for their preparation in which a hydrargillite-type aluminum oxide is milled, treated for 6 hours at 200 ° C. with a hydrothermal treatment with an aqueous solution of aluminum nitrate and formic acid, and the resulting product then calcined at 400 ° C to 1,300 ° C. The carrier material is

then extruded and ready for loading. As far as the nature and production of the catalyst support is concerned, reference is made to the two cited documents by way of reference.

There are no relevant requirements for the shape of the support material, but the spherical shape which can be used in reactors in the form of a bed and the honeycomb form which ensures a comparatively large surface area of the catalyst can be given as a suitable form.

In conventional applications of the catalysts mentioned, for example for hydrogenation reactions, carbon monoxide acts as a catalyst poison. In the investigations underlying this invention, however, it was surprisingly found that the noble metal catalysts could be used in hydrogen-rich gas mixtures, without significant losses in the effectiveness of the catalysts was observed. Furthermore, under the

It was observed that the catalysts could also be fed with oxygen-containing gas mixtures without dangerous mixtures of oxygen and hydrogen being observed in the product. Instead, it has been observed that the oxygen is reacted with hydrogen under the action of the catalyst with hydrogen, so that contained in the reactor-containing from the catalyst-containing gas mixture was only a very small proportion of oxygen (<0.01 vol.%).

The catalytic conversion of oxygen and hydrogen is also associated with the advantage that the catalyst and the gas mixture is heated by the waste heat of the oxyhydrogen gas reaction, so that an external heating of the catalyst (after it has reached its optimum operating temperature) is no longer required. In addition, the hot exhaust gas can be used via a heat exchanger to heat the gas flow for the catalyst-containing reactor, resulting in a further energy savings. Therefore, in the present invention, the hydrogen-rich gas preferably contains a proportion of oxygen. As a hydrogen-rich gas comes within the scope of the present invention, for. Eg metallurgical gas; Reduction gas or synthesis gas into consideration, as special

but suitable gas is coconut gas. The gas moreover advantageously contains a proportion of hydrocarbon constituents of at most 50% by volume, preferably at most 40% by volume and most preferably at most 30% by volume.

The hydrogen-rich gas also contains sulfur-carbon compounds as indicated. As sulfur-carbon compounds are primarily carbonyl sulfide (COS) and carbon disulfide (CS ₂ ), but also aromatic sulfur compounds such as thiophenes or aliphatic sulfur compounds such as mercaptans into consideration. As the usual content of carbonyl sulfide, a range of 1 to 100 ppm, and more preferably 10 to 50 ppm can be given. As the usual content of carbon disulfide, a content of 10 to 200 ppm, and more preferably 5 to 100 ppm can be given. The usual total content of sulfur-carbon compounds in the hydrogen-rich gas can be stated to be from 20 to 300 mg / Nm.sup.3 and in particular from 20 to 200 mg / Nm.sup.3.

Furthermore, the hydrogen-rich gas preferably contains oxygen. As the usual oxygen content, a range of 0.2 to 3.0 vol.%, And more preferably 0.4 to 1.5 vol.%.

As mentioned above, the stated catalysts work in

Gas atmospheres containing significant amounts of carbon monoxide, without restrictions. It may therefore be preferred if the hydrogen-rich gas contains carbon monoxide, suitably in an amount of 1 to 20 vol .-% and in particular 1 to 10 vol .-%.

The coke oven gas to be included in the process according to the invention is expediently produced by dry pyrolysis of hard coal, in which a

Gas mixture containing as main constituents hydrogen, methane, nitrogen and carbon monoxide and as minor constituents carbon sulfides is obtained. In the dry distillation or pyrolysis of hard coal, which is carried out at 900 to 1400 ° C, the volatiles of the coal are released and it forms porous coke, the substantially only

Contains carbon. The raw gas is then fractionated

Condensation in tar, sulfuric acid, ammonia, naphthalene, benzene and

Coke oven gas decomposed. As indicated above, the noble metal catalyst reductively converts oxygen contained in the gas mixture to water. As part of the

It is therefore preferable that the oxygen contained in the gas is simultaneously converted into water with the reduction of the sulfur-carbon compounds. It is particularly preferred if the oxygen contained in the gas is substantially, i. at least 80% by volume, preferably at least 90% by volume and more preferably at least 95% by volume, based on the total volume of oxygen in the gas mixture, is simultaneously converted to water with the reduction of the sulfur-carbon compounds.

On the other hand, within the scope of the present invention, it is not excluded that a portion or even a substantial portion (ie, at least 70% by volume, based on the total volume of oxygen in the gas mixture) of the oxygen will be removed from the gas mixture prior to reduction of the sulfur-carbon compounds or reacted with hydrogen to water.

The catalytic conversion of the sulfur-carbon compounds expediently takes place at a temperature of at least 150.degree. C. and preferably at least 200.degree. On the other hand, it is within the scope of the present

Invention preferably, when the catalytic conversion of the sulfur-carbon compounds at not more than 270 ° C, preferably at most 250 ° C and particularly preferably at most 230 ° C takes place. As a particularly favorable temperature range for the catalytic conversion of the sulfur-carbon compounds, the range of 200 ° C to 250 ° C and

in particular 200 ° C to 230 ° C exposed.

The catalytic conversion may further be in the range of 1 to 15 bar, i. H. be carried out both at atmospheric pressure or under pressure.

Preferred is an embodiment in which the pressure is in the range of about 1.2 to about 5 bar.

As indicated above, thermal energy is released as part of the reaction of oxygen in the gas mixture with hydrogen. It is therefore possible and preferred if the amount of oxygen in the hydrogen-rich gas is adjusted so that the energy released from the reaction is sufficient to keep the temperature at the desired level. For this purpose, z. B. the Amount of oxygen in the reaction mixture can be increased by the addition of oxygen, if appropriate.

Depending on the gas flow rate, the catalyst design and its construction, the reaction of the catalyst with the sulfur-carbon compounds in the hydrogen-rich gas may be incomplete, so that the gas resulting from the reaction has a content of sulfur-carbon compounds resulting in the further use of the gas makes a negative impression. It may therefore be useful if the catalytic conversion is followed by a stage in which still present in the gas mixtures sulfur-carbon compounds with a

Catalyst, which is not based on precious metals, in hydrogen sulfide

is converted. For this implementation z. For example, known cobalt-molybdenum catalysts or nickel-molybdenum catalysts in which the metals are present in sulfided form can be used.

The catalytic conversion converts carbon disulfide components contained in the hydrogen-rich gas into hydrogen sulfide (H ₂ S). The content of hydrogen sulfide is typically in the range of 50 to 300 ppm. The presence of H ₂ S is just as undesirable as that of carbon sulfides, but unlike the latter, it is possible

Hydrogen sulphide wash out relatively easily and, above all, quantitatively. For this purpose, the catalytic process is advantageously followed by a step in which hydrogen sulfide is removed by absorption in a basic medium from the gas mixture. This can be z. Example by means of an absorption column, through which the gases are passed, and in which the gases are treated, for example, in countercurrent with an aqueous base, such as sodium hydroxide or ammonia. Alternatively, however, other suitable for the purification of gases devices, such as Venturi scrubber. At low levels of hydrogen sulfide this can also be on a solid material, eg. B. in the form of zinc oxide adsorbed. From this, the H ₂ S can be released again in a regeneration phase.

The separated via the laundry or absorption hydrogen sulfide can then be converted via a conventional Claus process into elemental sulfur. Another aspect of the present invention relates to an apparatus for carrying out a method as described above, the apparatus comprising a hydrogen-rich gas feed 1, a reactor 2 containing a noble metal catalyst, a gas discharge from the reactor 3, and an apparatus for the separation of hydrogen sulfide from the gas 4, which is the discharge for gas from the reactor in the flow direction

is downstream.

The reactor is expediently a fixed bed reactor in which the catalyst is present in particulate form as a loose bed or solid packing. Since bedding more easily lead to channeling and thus to an inhomogeneous flow profile, the embodiment in which the catalyst is arranged in packages in the reactor, is preferred. Another advantage of a catalyst form in packages is the lower pressure drop.

The advantage of the hydrogenation in the fixed bed reactor is that high space-time yields can be achieved, which is why the inventive

Method can be carried out even at high GHSV values of about 5,000 to about 30,000 1 / h, and preferably about 10,000 to about 20,000 1 / h. Another advantage is that no special measures for the product discharge are required because the hydrogen-rich gas is preferably fed to the bottom of the reactor, the catalyst bed flows through, where it comes to the hydrogenation, and exits as a product at the top of the reactor.

The device described is expediently further designed such that the device for separating hydrogen sulphide from the gas 4 is designed as a gas scrubber with a liquid basic medium or as an adsorption stage for hydrogen sulphide with a solid adsorption medium.

Alternatively or additionally, the device described may advantageously be further developed in that it comprises a reactor for the reduction of sulfur-carbon compounds to hydrogen sulfide 6, which contains a catalyst which is not based on noble metals, and the reactor with the noble metal catalyst 2 in the flow direction is downstream.

In the foregoing it has been stated that the reduction of sulfur-carbon compounds for optimal conversion to hydrogen sulfide a certain temperature, for. B. at least 150 ° C, requires. To start from the beginning as complete as possible

To ensure carbon disulfide compounds to hydrogen sulfide, it is therefore expedient if the device according to the invention a

Heat exchanger 5, which is connected upstream of the supply line for hydrogen-rich gas 1 in the flow direction.

For monitoring the temperature in the reactor 2, the device according to the invention can also have a temperature measuring device with which the temperature can be determined. In order to allow control of the temperature over the amount of oxygen in the hydrogen-rich gas, the supply line for hydrogen-rich gas 1 with a controllable feed device for

Oxygen be connected, this is suitably controlled by a control circuit which is connected to the temperature measuring device.

In addition, the heat exchanger may be configured to use the gas discharged from the reactor 3 via the gas discharge for heating the gas to be supplied to the reactor.

Another aspect of the present invention relates to the use of noble metal catalysts for the simultaneous hydrogenation of sulfur-carbon compounds and oxygen in a hydrogen-rich gas to hydrogen sulfide and water, wherein the hydrogen-rich gas contains at least one compound selected from the group comprising COS and CS ₂ . For preferred embodiments of the noble metal catalyst and the

hydrogen-rich gas, the above statements apply analogously.

The essential advantage of the method according to the invention is that contents of sulfur-carbon compounds of about 50 to 300 ppm can be reduced to a residual content of the sulfur-carbon compounds of less than 1 to 5 ppm, preferably about 1 to 2 ppm

Oxygen content in the gas can be lowered to an unproblematic level. Another advantageous aspect is that hydrogenated or oxidized by the catalyst unsaturated hydrocarbons, which may also be present in Kokereigas, so that coking in downstream units (catalysts) can be avoided. Brief description of the drawings.

Figure 1 shows an embodiment of the present invention comprising a reactor 2 containing a noble metal catalyst, a hydrogen-rich gas inlet 1, a gas discharge from the reactor 3, and a downstream hydrogen separation device from the gas 4. Figure 2 shows another embodiment of the present invention comprising a reactor downstream of the reactor 2 for the reduction of sulfur-carbon compounds to hydrogen sulphide 6 containing a catalyst which is not based on noble metals.

LIST OF REFERENCE NUMBERS

1 supply line for hydrogen-rich gas

2 reactor

3 discharge for gas

4 Apparatus for the separation of hydrogen sulfide

5 heat exchangers

6 reactor for the reduction of sulfur-carbon compounds

Claims

claims

A process for the separation of sulfur from a hydrogen-rich gas having a proportion of sulfur-carbon compounds and oxygen, characterized in that a catalytic process for the reduction of sulfur-carbon compounds in hydrogen sulfide

is carried out, wherein the catalyst used is a noble metal catalyst and wherein the hydrogen-rich gas contains at least one compound selected from the group comprising COS and CS ₂ .

2. The method according to claim 1, characterized in that the catalyst used is a palladium and / or platinum catalyst, preferably on a solid support material.

3. Process according to claim 1 or 2, characterized in that the gas to be included in the process is coke oven gas.

4. The method according to any one of claims 1 to 3, characterized in that the oxygen contained in the gas simultaneously with the reduction of

Sulfur-carbon compounds is converted into water.

5. The method according to any one of the preceding claims, characterized

characterized in that the catalytic process, a stage

downstream of which hydrogen sulfide is removed by absorption in a basic medium from the gas mixture or carried out as adsorption stage for hydrogen sulfide with a solid adsorption medium.

6. The method according to any one of the preceding claims, characterized

characterized in that the catalytic process, a stage

downstream, in which still existing in the gas mixture sulfur-carbon compounds with a catalyst that is not based on precious metals, are converted into hydrogen sulfide.

7. The method according to claim 6, characterized in that it is based on the catalyst, which is not based on precious metals, a sulfidic cobalt-molybdenum catalyst or nickel-molybdenum catalyst.

8. The method according to any one of the preceding claims, characterized

characterized in that the hydrogen-rich gas for the catalytic process is heated to a temperature of at least 150 ° C and preferably 200 ° C to 250 ° C.

9. Use of noble metal catalysts for the simultaneous hydrogenation of sulfur-carbon compounds and oxygen in one

hydrogen-rich gas to hydrogen sulfide and water, wherein the hydrogen-rich gas contains at least one compound selected from the group comprising COS and CS ₂ .