TW381043B - Method for removing sulfur-containing contaminants, aromatics and hydrocarbons from gas - Google Patents

Abstract

The invention relates to a method for removing sulfur-containing contaminants in the form of mercaptans and H2S from a hydrocarbon gas, which may also contain CO2 and higher aliphatic and aromatic hydrocarbons, and recovering elemental sulfur, wherein in a first absorption step the sulfur-containing contaminants are removed from the gas, to form on the one hand a purified gas stream and on the other hand a sour gas, which sour gas is hydrogenated in order to convert the greater part of the mercaptans to H2S, whereafter the hydrogenated sour gas is fed to a second absorption stage in which the sour gas is separated into an H2S-enriched first gas stream, which is fed to a Claus plant, followed by a selective oxidation step of H2S to elemental sulfur in the tail gas, and an H2S-reduced second gas stream, which second gas stream is combusted.

Description

V. Description of the invention (/ z) The Claus unit 14 is expected to be converted into the element tellurium, which is a large part of the sulfur compounds, which is discharged through the pipeline 15. The regenerated absorbent is circulated to the second absorber 7 and returned to the pre-absorber 2. The cycle is filled with H 2 S and CO 2 absorbent via the generator 10 in the pipeline 10 via the pipeline _ post-secondary and ❸ ^ iktj 12 times. In order to increase the efficiency of the Claus plant, the exhaust gas is often passed to the exhaust gas sulfur removal stage 18 through a pipeline 16. This sulfur removal stage may be a known method for removing thorium, for example, a dry bed oxidation stage, an absorption stage, or a liquid oxidation stage. The air required for the oxidation is supplied via a line 17. The formed sulfur is discharged through a pipe 19. Then, before the gas is discharged through the chimney 22, the gas is passed from the pipe 2Q to the afterburner 21. The invention is illustrated by the following non-limiting examples. Example 1 A large amount of 15545 Nm3 / hour from a regenerator of a gas purifying device has a composition of 40 deg. C and 1.70 absolute bar pressure at the following composition. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs ^ 9. 0% by volume S 60 PP 丨 m by volume COS 0 .22% by volume ch3 SH 0 · 38% by volume C3 Hs SH 0. 03% by volume C3 h7 SH 0 · 0 1 Volume% C4 h9 SH 8 1 .53 Volume% C〇2 4 · 23 Volume% Hz 0 14- This paper size applies to China National Standard (CNS) A4 (210X 297 mm) Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Bag A7 B7 'V. Description of the invention (j) The present invention relates to a purified gas (especially a hydrocarbon gas such as natural gas, which is contaminated by sulfur compounds μ in the form of Η 2 S and thiols and by C ϋ 2 ) Method: More specifically, the present invention includes a method for converting thiols to H 2 S, and removing co 2 from H 2 S-containing gas, absorbed hydrocarbons, and aromatic compounds M forming elements from H 2 S Sulfur method: In the purification of natural gas, the purification of oil and gas and the purification of synthesis gas, sulfur-containing gas, especially H2S, is released, which should be restricted μ to remove especially the sulfur compounds formed during combustion S 0 2 row The extent to which these sulfur compounds are removed from, for example, natural gas in the atmosphere depends on the gas and quality requirements to be used: When the nitrogen gas must meet the so-called "pipeline specifications", the K2S content should be reduced to less than 5 mg / The value of Ν «ι3. The requirements also set the maximum content of other sulfur ib compounds: many methods are known from previous techniques, by which the amount of sulfur compounds in the gas (such as natural gas) can be reduced. To remove sulfur-containing components from the gas, column F is usually used Method path · In the first step, the pure ib gas to be processed is used to remove sulfur-containing components from the gas, and then the sulfur-containing components are recovered from the sulfur-containing components. Then, the sulfur-purified ib step of the residual gas follows this sulfur-purified ib step. Try to recover the final percentage of sulfur before the residual gas is discharged to the atmosphere through the chimney: In the purification step, a method in which an aqueous solvent (absorbent) is usually used is used. These methods are divided into five main groups, namely the chemical solvent method, the physical solvent method, the physical / chemical solvent method and the oxidation migration method, whereby the H2S is directly oxidized into sulfur in the water-soluble fatigue and the final fixed bed method. Paper size applies to China National Standard (CNS) Α4 specification (210 × 297 mm) (Please read the precautions on the back before filling this page)

、 1T amendment Year / A7 B7 V. Description of the invention (G) Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs Supply 3 10 Ν π 3 / hour air to this gas. The inlet temperature of the selective oxidation reactor is 2 2 P, C, and the outlet temperature is 292 ° C. The selective oxidation reactor is filled with a body as described in European patents Nos. 2 42. 3 2 β and 4 C 9. 3 5 3 and in International Patent Application No. W- A 3 5 / G 7 8 5 6劏. The sulfur formed in the sulfur recovery unit is concentrated and discharged after each stage. The inert gas is discharged into the soot through post-combustion. The amount of sulphur was 204 kg / h. The initial desulfurization efficiency of K based on high-sulfur gas (which contains 9. Q% by volume of H 2 S) was 97.7%. , 〆 广 * Brief Description of Drawings Figure 1 shows a block diagram of removing sulfur-containing pollutants from a hydrocarbon gas. Figure 2 shows an alternative specific spring embodiment of the present invention. Schematic component symbol description Figure 1: 1 pipeline 11 Claus unit 2 pipeline 12 pipeline 3 hydrogenation reactor 13 pipeline 4 pipeline 14 tail gas sulfur removal stage 5 evaporator 15 pipeline 6 pipeline 16 pipeline 7 Pipe 17 Pipe 8 Pipe 18 Afterburner 9 Absorption / regeneration device 19 Soot 10 Pipe -17- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) ----- ---------------- Order · ------- · (Please read the precautions on the back before filling out this page) Printed by A7, Consumers Cooperative of the Central Standards Bureau, Ministry of Economic Affairs B7 V. Description of the invention (>) This Η 2 s is like chemical or physical absorption or adsorption or selective catalytic oxidation. The first three groups mentioned above are generally used in industrial K to remove a large amount of sulfur-containing components, most of which are found in ordinary large amounts of gas. in. The latter two groups are limited by the amount of sulfur to be removed and the concentration of sulfur-containing components. Therefore, these methods are less suitable for the removal of high-concentration sulfur in a large amount of industrial gas pure ib devices. These chemical solvent methods include the so-called amine method, in which an aqueous solution of an alkanolamine or potassium carbonate solution is used. Use different chemicals. For example, polyethylene glycol (DMPE6) under the Selexol name * -Methyl-pyrrolidine surface (NMMP) known as the Purisol name, or methanol known as the Rectis ο 1 name: in Physics / Chemistry In the group of methods, the Su 1 fi η ο 1 method is known: In this method, a mixture of alkanolamine and cyclobutane dissolved in a small amount of water is used = In the above three methods, an absorption device and Regenerator: In the absorption device, these sulfur-containing components are chemically or physically bound to the solvent. The sulfur-containing components are desorbed from the solvent by pressure reduction and / or temperature increase in the regenerator, and then dissolved and reused: For a detailed description of this method, see R. X. M ed ο X ” Stinking "(6 (118 & 11 () 1 ^ [1111 (18 ^ 6〇_10-II ing) Campbell Oil Series (C ambe 1 1 P i? Tr ο 1 eum) (1 9 7 7) In this method, in addition to these sulfur-containing components, C02 is also removed in whole or in part. Depending on the selected solvent, the sulfur-removed compounds and C 0 2 flow from the regenerator to the sparse recovery-4 -This paper size is in accordance with Chinese National Standard (CNS) A4 (210X297 mm) n ^ 1. ^ 1 Sale ^ jll 1. ^ 1 ml. ^ 1 ^ 1 n ^ i One shovel 1 ^ 1 (Please read the back first (Notes for filling in this page)

V. Description of the invention (A Λ7 B7

Figure 2 Kushiro I 2 Piping 2 Pre-absorber 13 Piping Kuss 14 Claus unit 4 Pipe 15 Pipe 5 Hydrogenation reactor 16 Pipe 6 Pipe 17 Pipe 7 MU Wide range grazing device 18 Exhaust gas Sulfur removal i Section S-pipeline 19 pipeline 9 regenerator 20 pipeline 10 pipeline 2 1 afterburner 1 1 pipeline 22 chimney ------, -------- installation *- ------ Order --------- Line (Please read the notes on the back before filling out this page) Printed by Bei Gong Xiao F Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 18- This paper size applies to China Standard (CNS) A4 specification (210 X 297 public love) A7 B7 printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. 5. Description of the invention (i) The device M recovers the sulfur from H2S and other sulfur compounds. Once used to recover sulfur compounds obtained in this way, especially Hz S, the common method for recovering sulfur is the C 1 aus method. This method is described in detail by K. G · Paska] 1 The Effectiveness of the Law of Crowe ", Western Research Development (C apabi 1 i t. Y 〇f the modified Claus process; Western Research Dev ev e-1 ο P ni en t.), C a 1 gary, Λ 1 berta, Canada , I 9 7 9 years. The Claus process consists of a thermal step typically followed by 2 or 3 reactor steps: in the thermal step, one third of the H2S is burned to SO2 according to the following reaction

Hz S + 1.5 0 2-> S02 + Hz 0 Then the residue, that is, 2/3 of &gt; H2, reacts with the formed S02, and according to the Claus reaction, sulfur and water are formed: 2 Η 2 S + S 〇2-&gt; 3 S + 2 Η 20 The efficiency of the Claus method depends on many factors: for example, the balance of the Claus reaction makes the increase in the water content of the gas shift to H2 S. Question: Sulfur The efficiency of the recovery device can be increased by using a tail gas sulfur recovery device; the known methods are the SUPERCLAUS method and the SC 0 Τ method: used in the SU ΡΕ β CLAUS method as in European Patent Application No. 2 4 2. 9 2 G And 4 0 9. 3 553, M and the ib catalyst described in the international patent application WO-A 95.G7856, especially as "Carbon M ib compound treatment" 1 April 1989, No. 4 I]-4 The catalysts described on page 2 are used in the third or fourth reactor stage: Using this method, the last residue of Η 2 S present in the process gas stream is selectively oxygenated according to the following reaction it 成 Elemental sulfur-5-This paper is sized for China National Standard (CNS) A4 (210X297 mm)-^ 1 ....... 1 n II- ! I --II 士 5-〆I ^^ 1 H— n ^ i--I----(Please read the notes on the back before filling out this page) Printed by the Consumers Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (f) Η 2 S + 0.000 z —> S + Hz 〇 In this way, the efficiency of the sulfur recovery unit can be easily increased to 99.5% 'Feed to Claus The gas of the device can sometimes contain a large amount of c 0 2, for example up to 38.5%, which has a very detrimental effect on the flame temperature in the thermal step. A large amount of C 02 can cause the flame instability and the thermal step in the thermal step. The efficiency will be reduced, and the overall efficiency of the M Claus unit will be reduced: that is, the gas may contain a large amount of hydrocarbons. When oleophobic gas is processed in oil refining oil and gas, the content of hydrocarbon compounds is usually low, and most <2% by volume. In the purification of natural gas, physical or physical / chemical methods are used because The results of larger amounts of hydrocarbons and aromatics can end in the gas (Claus Nitrogen) that is passed to the sulfur recovery unit .: Because the reaction rate of hydrocarbons with oxygen is higher than the reaction of Η 2 S and oxygen These hydrocarbons are completely burned during the hot phase of the Claus plant. When a large amount of CO is present, the flame temperature will be relatively low, and therefore the rate of component reactions during combustion will also be reduced. : As a result, soot formation may occur in the flame of the combustion furnace in the hot stage. Soot formation may cause clogging in the catalyst reactor (especially the first reactor) of the Claus plant. That is, the ratio between the oxygen required for the conversion of h2S to sulfur and the oxygen required for the combustion of hydrocarbons and aromatic ib compounds can occur at values that the Claus method is no longer properly controlled: these The problem is known in the industry: In addition, except for ii 2 s and the large amount of C 0 2 mentioned above, the mercaptan is also usually -6-This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) i ^ i «HI ml -1 n ^ — n · ^ nn I In— ^ J ^ nn ^^^ 1 1 ^ 1-'^^ (Please read the notes on the back before filling this page) Central Bureau of Standards, Ministry of Economic Affairs Printed by employees' consumer cooperatives A7 B7 5. The invention description (ζ) exists in the gas. In the industry, chemical methods are used in which these mercaptans are not removed from the gas to be purified (such as natural gas), so it is necessary to make the fixed bed method purify afterwards. Usually molecular sieves are used to remove these thiols. However, when the fixed bed is saturated with thiols, the molecular sieves must be regenerated, and purified natural gas is often used for this purpose, and then the regeneration gas should be purified sequentially. In the regeneration of molecular sieves, most of these mercaptans are released at the beginning of regeneration: there is also a method in which mercaptans are returned to the Claus unit from the post-purification stage and then these mercaptans are in the hot stage of the Claus unit The air control caused by the peak load in the air was severely disturbed: this method path was described in the Journal of Oil and Gas (0 i 1 and G as J 〇urna 1) 5 7, August 13th, 1991 «第 57— P. 59. Furthermore, this leads to the loss of natural gas, which can easily reach about i 0%. 'A method is known for treating sulphur-containing gases containing carbonyl sulphides and / or other organic components such as mercaptans and di-fluorenyl disulfide (b)' This method is described in British Patent No. 1 5 6 3 2 5 It is an object of the present invention in No. 1 and British Patent No. 147 to 950 to provide a hydrocarbon gas (such as natural gas, which may also contain CO2 and higher aliphatic and aromatic hydrocarbons). ) A method for removing sulfur-containing pollutants and elemental sulfur recovery in the form of mercaptans and ii2 s, wherein the method does not suffer from the disadvantages listed above: more specifically, the object of the present invention is to provide a method whereby the exhaust gas is not included or only Very few harmful substances Z method, so it can be discharged into the atmosphere without being affected by this paper size. Applicable to China National Standard (CNS) A4 specification (210X297). ---------- ^- ------ Order ----- ^ (Please read the notes on the back before filling out this page) A7 B7 printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Statement of Invention (i-) Any objections: It is also an object of the present invention to provide such sulfur-containing pollutants A method for recovering a large amount of elemental sulfur, such as up to more than 90%, and more particularly more than 35% ◊ The present invention provides a simple method for recovering pure it contaminated hydrocarbon gas using sulfur &gt; According to this method, In the first absorption step, these sulfur-containing pollutants are removed from the gas to form a purified gas stream on the one hand and a high-sulfur gas on the other hand. The hydrogen ib high-sulfur gas converts a larger part of the thiol into H2 S, then the hydrogenated high-sulfur gas is sent to the second absorption step, where the high-sulfur gas is divided into a H2S-rich first gas stream, which is fed into the Claus unit, followed by 12 S in the tail gas. Selective oxidation step to elemental sulfur, and a second gas stream that reduces H2S. Its second gas stream is burned: Surprisingly, using the method according to the invention, a large number of gas streams can be very efficient. According to the present invention, a high sulfur gas first passes through a hydrogenation reactor, and the mercaptans in these gases are converted into H due to the hydrogen supply ribs. z S: The high-sulfur gas is then divided into two in the concentrating unit. Other gases, that is, H 2 S-rich gas and C 0 2 -rich gas, which contain a large amount of C 0 2, hydrocarbons. Compounds and aromatics: C 0 2 -rich gases with the presence of hydrocarbons and aromatic ib compounds allow proper combustion in afterburners: The heat released in this afterburner can be used very effectively, for example with To generate steam:

The H2 S-rich gas is passed to the sulfur recovery unit. "Using this method, H2 S -8- This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) ^^ 1« mr— ^^^^ 1 n mu m ^ iB ^ ^ (Please read the notes on the back before filling out this page) Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (7) The concentration can be easily increased 2 to 6 times: The H2S gas can be processed well in the Claus unit. The big advantage is that most of C 0 2, hydrocarbons and aromatic compounds are not present, and no additional gas will pass through the unit during combustion. Amount. As a result, the Claus unit can be made with a much smaller design and achieve a much higher sulfur recovery efficiency: The tail gas from the Claus unit is further treated in the K-sulfur compound based on the selective oxidation of K sulfur compounds to elemental sulfur: tail gas The recovery unit is more like a SUPERCLAUS reactor stage: The exhaust gas from the tail gas desulfurization unit is burned in the afterburner: the released heat can be effectively used to generate steam. According to the present invention, the high sulfur gas is passed to the containing support together with hydrogen. The hydrogenation reactors of the Group 6 and Group 8 metal catalysts of sulfur on the support are used as supports, and oxygen ib aluminum with this type of catalyst is preferably used because this material, in addition to the required thermal stability, It can also increase the good dispersion of the active component: As a catalytically active material, it is preferred to use a combination of cobalt and molybdenum. In the hydrogenation step, the mercaptan in the hydrogen-assisted rib gas is converted to 1] 2 S: Unwanted reactions confined between Η 2 S and C 0 2 to C 0 S and Η 2 0. Water vapor is supplied in the hydrogenation step, so less C 0 S is formed to prevent tritium formation from C 0 S. Method, but without supplying water vapor, in order to install a pre-absorber before the hydrogenation stage, whereby the concentration of Η 2 S in the gas is reduced to less than a quarter: the gas from this pre-absorber is then passed to the hydrogenation reactor, by Because of the added hydrogen, all mercaptans are converted into paper. The paper size applies the Chinese National Standard (CNS) A4 (210 X 297 mm) m ^^^^ 1 ^^^^ 1 I ^^^^ 1 I n- ^ ϋ lit-aJIf ^ imn (Please read the precautions on the back before filling this page) β7 V. Description of the invention (δ) (Please read the precautions on the back & fill in 3 pages) H2 S. The residual HZ S is then selectively absorbed in the second absorber of the second absorption step. On equilibration, the same H2S enrichment is then obtained as if using a single absorber. However, using this method, the risk of C 0 S formation is completely or largely avoided. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs According to a preferred embodiment of the present invention, the first absorption step is performed using a chemical, physical or chemical / physical absorbent which removes all pollutants from natural gas. Preferably, this is a cyclobutane-based absorbent, combined with secondary and tertiary amines. As already indicated, the system is pure ib that is known and has been used for large amounts of natural gas, especially when the natural gas is liquefied after purification (such as the SULFINOL-D method). Absorption (as is conventional) is a system by which these pollutants are absorbed in the solvent of the first column, and then, when the solvent is loaded with the pollutants, this solvent is regenerated in the second column, for example Reduced by heating and / or by pressure. The temperature at which absorption occurs depends largely on the solvent and pressure used. At a circulation pressure of 2 to 100 bar of natural gas, the absorption temperature is usually 15 to 5 Q ° C, although good results can be obtained outside these ranges. It is better to purify the natural gas K to fit the specifications of the pipeline, which indicates that there may generally be no more than lQppra, and more particularly no more than 5 ports? ^ Of 112 3. The gas stream exiting from the first absorption / desorption contains most of the pollutants such as H2S, aromatics, hydrocarbons and thiols, and C0z, and then a suitable catalyst on alumina such as Hydrogenated in the presence of C o / MO and hydrogen. However, at the end, the gas flow should be heated from about 4 Qt: the absorption / desorption temperature to the temperature of 2 QQ to 3 fl Q ° C required for hydrogenation -1 0-This paper size applies Chinese National Standard (CNS ) Λ4 specification (210X297 mm) Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (Clever): This heating preferably occurs indirectly and does not use a burner arranged in the gas stream, as is known : In fact, the disadvantage of direct heating is that in this case direct heating causes substantial soot formation, which can lead to dirt and blockage in the action of hydrogen it: as already mentioned above, measures can be taken to reduce C 0 S formation: 'In the second absorption stage, the hydrogenated gas is divided into a gas rich in H2S and a gas reduced in H2S: This absorption preferably uses a solvent of M secondary or tertiary amine as the matrix, and more specifically methyldiethyl Aqueous amine solutions can optionally be combined with activators. Therefore, or using meta-cholesteryl tertiary amines. This method is known and described in the literature (M ϋ Ε Α method, ICARS 0 L, FL Ε XS 0 R Β-S Ε, etc.) . The method of operating this method can be more concentrated than the first absorption stage, and the degree of concentration is preferably at least 2 to 6 times or more. Its part depends on the initial concentration of H2S: the degree of concentration of ib can be determined by the appropriate structure of the absorber Select and set: The rich 2S gas is fed to the hot stage of the Claus plant. The device is known, and the method (in which the operating temperature and pressure of each phase) has been described in detail in the previously cited announcement: The tail gas from the Claus device, which still contains residual sulfur compounds, if If necessary, after supplemental hydrogenation, it is fed to an exhaust gas treatment unit, where elemental sulfur is formed via selective oxidation of sulfur compounds, which is suitable for separation in a device suitable for this purpose, such as in European Patent Application No. 6 5 After the separation of tellurium, as described in No. 5.4, the rest of the gas can be burned, can be selectively formed into steam, and discharged into the atmosphere; -1 1-This paper standard applies Chinese National Standard (CNS) A4 Specifications (210X 297mm) l ^ i ^^^ 1 m · tL ^ i HI I nn 1. ^^ 1 I HH n ^ i iin ^ i Λ ^ i \ (Please read the precautions on the back before filling (This page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs ^ A7 B7 V. Description of the Invention (β) Selective oxidation is preferably performed in the presence of a catalyst that selectively converts sulfur compounds into elemental sulfur, such as the Equal to the aforementioned The catalyst Chau and international patent applications described. These notices, the contents of which are incorporated herein by reference, also indicate the most appropriate method conditions, such as temperature and pressure. However, in general, the pressure is not important, and the temperature may be between the dew point of sulfur and about 3 G (TC, more particularly below 2 5 G ° C.) The invention will be described with reference to two figures Where the K block diagram describes the method according to the present invention. High tellurium gas flows from the first absorption unit (out of the day), where the contaminated natural gas is divided into one, the gas flow with the required specifications, and the other, High tellurium gas, before passing into the hydrogenation reactor 3, in the pipeline 1 to the required nitriding temperature, under the addition of hydrogen and / or carbon monoxide through the pipeline 2, that is, the water vapor is fed to In line 1, W inhibits the formation of carbonyl sulfides in hydrogenation reactor 3. In hydrogenation reactor 3, the tellurols and other phosphorus-sulfur compounds present in the gas are converted into H2S. From hydrogenation reactor 3 After cooling, the gas is passed to the absorber of the selective absorption / regeneration device via line 7. In this cooling, the supplied water vapor is concentrated and circulated to the hydrogenation reactor 3 via the evaporator 5. After the gas passes through the chimney 19 Before unloading, gas The non-absorptive component is mainly composed of carbon dioxide, hydrocarbons (including aromatic compounds) and low content of H2S, and goes directly to the afterburner 18 through the pipeline 8. The rich from the regeneration section of the absorption / regeneration device 9 The gas mixture of H2 S is supplied through line 10 -1 2--------- ^ ---- ------- ^ ------ Net (Please read the precautions on the back first (Ear fill in this page) This paper size is applicable to China National Standards (CNS) Λ4 specification (210X2W mm) Printed by A7 B7 of the Consumer Cooperatives of the China Standards Bureau of the Ministry of Economic Affairs. Unit η, where a large part of the sulfur compounds are converted into elemental sulfur, which is discharged through line 12. In order to increase the efficiency of the Claus unit, the exhaust gas is often passed through the line 1 3 to the tail gas sulfur removal stage 1 4: This sulfur removal stage may be a known sulfur removal method, for example, a dry bed oxidation stage, an absorption stage, or a liquid oxidation stage. The air required for the oxidation is supplied through a pipeline 15. The formed sulfur is supplied through a pipeline Road 16 unloading = Then before the gas is unloaded through the chimney 19, the gas passes through the pipe 17 to Afterburner 18. As shown in Figure 2, the high sulfur gas comes from the first absorption unit (not shown) (where the contaminated natural gas is divided into one with a gas flow of the required specification and the other with high sulfur Gas), through the pipeline 1 to the pre-absorber 2 of the absorption / regeneration device, further comprising a second absorber and the regenerator 9. The gas from the pre-absorber 2 is passed to the hydrogen ib reactor 5 through the pipeline 3 And by adding hydrogen and / or carbon monoxide via line 4 to the required hydrogenation temperature-in the hydrogenation reactor 5 the thiols and other organic sulfur compounds present in the gas are converted into hydrazone 2 S: from the hydrogenation reactor After cooling, the gas passes through the pipeline 6 to the second absorber: the unabsorbed component of the gas is essentially composed of carbon dioxide, hydrocarbons (including aromatic compounds) and a minimum amount of 12 S, Before the gas is discharged through the smoke letter 22, it is passed to the afterburner 2 1 through the line 8: the gas mixture rich in H 2 S comes from the regenerator 9 and is fed into the line 1 3 to 1 3-this paper standard applies China National Standard (CNS) Α4 Specification (210X2 97 mm) n ^ i ϋ · nn 1 ^ 1 n ^ — n ^^^ 1 nn ^ n · ϋ ^ — ^^^ 1 ^ / ^^^ 1 at ^^ i. Wu, \ έ 〆 (Please (Read the notes on the back before filling out this page)

V. Description of the invention (/ z) The Claus unit 14 is expected to be converted into the element tellurium, which is a large part of the sulfur compounds, which is discharged through the pipeline 15. The regenerated absorbent is circulated to the second absorber 7 and returned to the pre-absorber 2. The cycle is filled with H 2 S and CO 2 absorbent via the generator 10 in the pipeline 10 via the pipeline _ post-secondary and ❸ ^ iktj 12 times. In order to increase the efficiency of the Claus plant, the exhaust gas is often passed to the exhaust gas sulfur removal stage 18 through a pipeline 16. This sulfur removal stage may be a known method for removing thorium, for example, a dry bed oxidation stage, an absorption stage, or a liquid oxidation stage. The air required for the oxidation is supplied via a line 17. The formed sulfur is discharged through a pipe 19. Then, before the gas is discharged through the chimney 22, the gas is passed from the pipe 2Q to the afterburner 21. The invention is illustrated by the following non-limiting examples. Example 1 A large amount of 15545 Nm3 / hour from a regenerator of a gas purifying device has a composition of 40 deg. C and 1.70 absolute bar pressure at the following composition. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs ^ 9. 0% by volume S 60 PP 丨 m by volume COS 0 .22% by volume ch3 SH 0 · 38% by volume C3 Hs SH 0. 03% by volume C3 h7 SH 0 · 0 1 Volume% C4 h9 SH 8 1 .53 Volume% C〇2 4 · 23 Volume% Hz 0 14- This paper size applies to the Chinese National Standard (CNS) A4 specification (210X 297 mm) A7 B7 Staff consumption of the Central Standards Bureau of the Ministry of Economic Affairs Cooperative printed f-toluene 5. Description of the invention (丨) 3.51% by volume hydrocarbons (Ci to C! 7) 1.08% by volume 'aromatic compounds (benzyl, toluene, xylene) will be 3 0 0 G Ν πι3 / A reducing gas containing hydrogen and carbon monoxide is supplied to this high sulfur gas, and then heated to 2 Q 5 TJ MH in a hydrogenation reactor to hydrogenate all existing mercaptans to H 2 S, which includes sulfurized Group 6 and / Or Group 8 metal catalyst, in this case C ο-Μ 〇 catalyst: 7 0 0 〇 in3 / hour water vapor is also supplied to this high sulfur gas K inhibits the formation of C ϋ S in the hydrogenation reactor-from the reaction The temperature of the device gas is 22 6 C: then high The gas is cooled to 4 6 C, and the water vapor contained therein is condensed: this condensation is circulated via the evaporator to the high sulfur gas passing through the hydrogenation reactor: the amount of gas from the hydrogenation reactor, after the supplied water vapor condenses, Is 1 8 5 4 5 N m3 / hour and has the following composition:

8.08 vol% Η2 S

5 0 PP ra volume COS 6 9.7 8 volume% C 0 2 6.4 volume% H2 0 2.94 volume% hydrocarbon ib compounds (C! To C i 7) 0. Si volume% aromatics (benzene, toluene, 1.03 volume) % Η 2 10.86% by volume, N2 The cooled gas in the absorber of the gas pure ib device and the size of the paper are applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -------- ---- t-shirt ----- jiT ------ ^ (Please read the notes on the back before filling in this page) ΑΊ Β7 V. Description of the invention (Printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs II 7 Alcohol amine solution is contacted, whereby Η 2 S and-part of C0 2 are absorbed by the product gas of the Songbai absorber (C (h: rich gas, the amount of 丨 is 1)) 680 Νί J3 / hour and has The following composition: 7 4 .54% by volume C 0 2 500 PP Π1 by volume '2 S 8 0 PP m by volume COS 6.7 8% by volume H2 0 3. 48% by volume hydrocarbon it compounds (C 1 to C! 1) 1.07 vol% aromatic Compounds (benzene, toluene, xylene) 1.2 1 vol% h2 12 .86 vol% n2 After post-combustion, this gas is passed to the chimney to be desorbed in the regenerator ~ y post-sulfur 2 S / C. 2 Gas mixture (2 S rich gas) Pass to sulfur recovery unit-this 2 S / C0 2 gas mixture. The material is measured to 2870 Nm for 3 hours and at 40 T: and 1. 7 absolute bar has The following composition = 5 1. 9 vol% Hz S 43.8 vol% CO 2 4. 3 vol% Hz 0 Supply 2 9 7 δNιη3 / hour air to the burner in the hot stage of the sulfur recovery unit After the two Claus reactor stage 1 there are 1.14 vol% Hz S and 0.07 vol% S0 2_ mj in the process gas, and then the side i gas is fed to the tail gas removal stage, by selective h2 S oxidized anti-m heart dagger, device binding '\ (Please read the precautions on the back before filling this page) This paper size applies to China Home Standard (CNS) A4 size (210X297 mm) said the amendment date / A7 B7 V. description of the invention (G) Ministry of Economic Affairs Intellectual Property Office employees consumer cooperatives will be printed 3 10 Ν πι3 / hour air supply to this gas. The inlet temperature of the selective oxidation reactor is 2 2 P, C, and the outlet temperature is 292 ° C. The selective oxidation reactor is filled with a body as described in European patents Nos. 2 42. 3 2 β and 4 C 9. 3 5 3 and in International Patent Application No. W- A 3 5 / G 7 8 5 6劏. The sulfur formed in the sulfur recovery unit is concentrated and discharged after each stage. The inert gas is discharged into the soot through post-combustion. The amount of sulphur was 204 kg / h. The initial desulfurization efficiency of K based on high-sulfur gas (which contains 9. Q% by volume of H 2 S) was 97.7%. , 〆 广 * Brief Description of Drawings Figure 1 shows a block diagram of removing sulfur-containing pollutants from a hydrocarbon gas. Figure 2 shows an alternative specific spring embodiment of the present invention. Schematic component symbol description Figure 1: 1 pipeline 11 Claus unit 2 pipeline 12 pipeline 3 hydrogenation reactor 13 pipeline 4 pipeline 14 tail gas sulfur removal stage 5 evaporator 15 pipeline 6 pipeline 16 pipeline 7 Pipe 17 Pipe 8 Pipe 18 Afterburner 9 Absorption / regeneration device 19 Soot 10 Pipe -17- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) ----- ---------------- Order · ------- · (Please read the precautions on the back before filling this page)

V. Description of the invention (A Λ7 B7

Figure 2 Kushiro I 2 Piping 2 Pre-absorber 13 Piping Kuss 14 Claus unit 4 Pipe 15 Pipe 5 Hydrogenation reactor 16 Pipe 6 Pipe 17 Pipe 7 MU Wide range grazing device 18 Exhaust gas Sulfur removal i Section S-pipeline 19 pipeline 9 regenerator 20 pipeline 10 pipeline 2 1 afterburner 1 1 pipeline 22 chimney ------, -------- installation *- ------ Order --------- Line (Please read the notes on the back before filling out this page) Printed by Bei Gong Xiao F Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 18- This paper size applies to China Standard (CNS) A4 specification (210 X 297 public love)

Claims (1)

6. Scope of patent application 1. A kind of sulfur-containing pollutants and recovered elements removed from sulfur enzymes and HZ S from hydrocarbon gas (which may also contain CO2 and higher fats and aromatic hydrocarbons) Method, in which the sulfur-containing pollutants are removed from the gas in the first absorption stage, M-forms a purified gas stream on the one hand and high-sulfur gas on the other hand «* its high sulfur gas is hydrogenated to make it larger Part of the tellurium fermentation converts H2S, and then feeds the hydrogenated high sulfur gas to the second absorption stage, where the high sulfur gas is separated into a first H2S rich gas stream, which is fed to a Claus unit, and then in Stage of selective oxidation of Sg elemental sulfur in tail gas, and a second gas stream that reduces H2S, which is burned. 2. The method according to item 1 of the patent application range, wherein the first absorption step is performed using a chemical, physical, or chemical / physical absorbent, which substantially removes all tellurium compounds and CO 2. 3. The method according to item 2 of the patent application, wherein the absorbent is based on cyclobutane and combined with a secondary or tertiary amine. 4. The method according to item 1 or 2 of the scope of patent application, wherein the second absorption step is performed using an absorbent based on secondary and / or tertiary amines. Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the notes on the back before filling this page) 5. According to the method of item 1 or 2 of the scope of patent application, the first absorption step is performed when the gas contains no more than lOppm, more particularly the method of thorium-containing pollutants not exceeding 5ppra. 6. The method according to item 5 of the application, wherein the gas. Is natural gas, which can be selectively liquefied after purification. 7. The method according to item 1 or 2 of the scope of patent application, in which the second absorption step This paper size applies the Chinese National Standard (CNS) Λ4 specification (210X 297 mm) 6. Scope of patent application 1. A kind of sulfur-containing pollutants and recovered elements removed from sulfur enzymes and HZ S from hydrocarbon gas (which may also contain CO2 and higher fats and aromatic hydrocarbons) Method, in which the sulfur-containing pollutants are removed from the gas in the first absorption stage, M-forms a purified gas stream on the one hand and high-sulfur gas on the other hand «* its high sulfur gas is hydrogenated to make it larger Part of the tellurium fermentation converts H2S, and then feeds the hydrogenated high sulfur gas to the second absorption stage, where the high sulfur gas is separated into a first H2S rich gas stream, which is fed to a Claus unit, and then in Stage of selective oxidation of Sg elemental sulfur in tail gas, and a second gas stream that reduces H2S, which is burned. 2. The method according to item 1 of the patent application range, wherein the first absorption step is performed using a chemical, physical, or chemical / physical absorbent, which substantially removes all tellurium compounds and CO 2. 3. The method according to item 2 of the patent application, wherein the absorbent is based on cyclobutane and combined with a secondary or tertiary amine. 4. The method according to item 1 or 2 of the scope of patent application, wherein the second absorption step is performed using an absorbent based on secondary and / or tertiary amines. Printed by the Consumers' Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the notes on the back before filling this page) 5. According to the method of item 1 or 2 of the scope of patent application, the first absorption step is performed when the gas contains no more than lOppm, more particularly the method of thorium-containing pollutants not exceeding 5ppra. 6. The method according to item 5 of the application, wherein the gas. Is natural gas, which can be selectively liquefied after purification. 7. The method according to item 1 or 2 of the scope of patent application, in which the second absorption step is based on the Chinese National Standard (CNS) Λ4 specification (210X 297 mm) A8 B8 C8 D8 6. The scope of patent application is carried out in the first A method in which the Hz S content in a gas stream is at least 2.5 times, and more particularly at least 4 times higher than the H 2 S content in a high sulfur gas. 8. A method according to item 1 or 2 of the scope of the patent application, wherein the content of mercaptans in the hydrogenated gas stream is less than 1 ppm. 9. The method according to item 1 or 2 of the scope of the patent application, wherein the hydrogenation occurs on the support catalyst, and the group is selected from a group VIB gold tincture and at least one group VIII. Metals, and more particularly the combination of M cobalt and molybdenum, are the catalytically active components of the matrix. {Please read the notes on the back before filling this page) '1T Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs This paper size applies to the Chinese National Standard (CNS) Λ4 specification (210 × 297 mm)