CN109019524B - Sulfur recovery process for acid gas with medium and low concentration - Google Patents
Sulfur recovery process for acid gas with medium and low concentration Download PDFInfo
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- CN109019524B CN109019524B CN201811005747.0A CN201811005747A CN109019524B CN 109019524 B CN109019524 B CN 109019524B CN 201811005747 A CN201811005747 A CN 201811005747A CN 109019524 B CN109019524 B CN 109019524B
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- C01B17/00—Sulfur; Compounds thereof
- C01B17/02—Preparation of sulfur; Purification
- C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
- C01B17/0404—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process
- C01B17/0426—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process characterised by the catalytic conversion
- C01B17/0434—Catalyst compositions
Abstract
The invention provides a sulfur recovery process of acid gas with medium and low concentration, which is used for treating H-containing gas2S20-50v% acid gas, the main equipment comprises sequentially-connected acid gas flow direction burningThe system comprises a burning furnace, a two-stage Claus reactor, a selective hydrogenation reduction reactor, a selective oxidation reactor, a circulating absorption unit and a liquid sulfur tank; the circulating absorption unit comprises an absorption tower, circulating absorption liquid is alkali-containing liquid and/or calcium-containing liquid, and the main water source is condensed water of steam contained in the process gas. The process of the invention comprises the steps of introducing COS and CS into a first-stage Claus reactor2Fully hydrolyzing, selectively oxidizing the H in the reactor2S is close to total conversion, small amount of SO2The treatment in the absorption tower realizes the ultralow atmospheric emission; the sulfur collected by the condensed water or the absorption liquid has high purity; the circulating absorption liquid and the residual liquid have low concentration and are sent to a sewage device and a coal-fired boiler flue gas wet desulphurization unit for treatment or sent to the coal-fired boiler as coal water spraying.
Description
Technical Field
The invention relates to a sulfur recovery process, in particular to a sulfur recovery process for acid gas with medium and low concentration.
Background
In the process of petrochemical industry, coal chemical industry and coal gas production, most of sulfur contained in raw materials is usually converted into H2S, separating to form H-containing2Acid gas of S; h is often separated and formed in the process of purifying natural gas2Acid gas of S. These acid gases are typically treated by a sulfur recovery process to recover H2S is converted to elemental sulphur as much as possible.
The acid gas sulfur recovery device is used for recovering the SO of tail gas exhausted from a chimney in the operation process2The concentration is a continuous monitoring project, and in recent years, the emission requirement is more strict, for example, the emission standard of pollutants for petroleum refining industry (GB31570-2015) specifies SO of an acid gas recovery device2Emission concentration limit of 400mg/m3The development density is already high at the state and the bearing capacity of the resource environment begins to weakenRegional or regional SO with small capacity of atmospheric environment, fragile ecological environment, easy occurrence of serious environmental pollution problem and need of special protective measures2Emission concentration limit value is 100mg/m3. Due to H2S、COS、CS2Is a main foul odor pollutant, and the emission concentration should be reduced as much as possible. Some regions also implement more stringent emissions standards or are rewarded with penalties based on emissions.
The acid gas sulfur recovery process in the prior art comprises a combustion furnace, a two-stage Claus reactor, a selective hydrogenation reduction reactor, a selective oxidation reactor and a deep purification unit along the flow direction of acid gas, wherein hydrogen sulfide contained in the acid gas is basically converted into sulfur for recovery, and then the process gas reaches the emission standard and is exhausted through a chimney. Wherein the selective hydrogenation reduction reactor is used for reducing SO contained in the process gas2All reduction to form elemental sulfur and a small amount of H that can be processed in a subsequent selective oxidation reactor2S, the organic sulfur contained is converted into elemental sulfur or H as much as possible2S; o-selective oxidation reactor by introducing air make-up2H is to be2S is basically converted into elemental sulfur, the elemental sulfur is selectively oxidized into the elemental sulfur, and a small amount of SO is generated as a byproduct2The idea of process control is to produce less SO on the premise of ensuring the yield of elemental sulfur2Is the main objective to obtain higher H2Off-gas H with a moderately low S conversion2S content is a secondary target, and H in the process gas at the outlet of the selective oxidation reactor2The S content is usually SO2Several times higher than the content of H in the deep purification unit2S is oxidized into elemental sulfur and is recycled, and part of SO is simultaneously used2And (4) disposing. The deep purification unit can adopt a dry active carbon desulfurizer such as loaded alkali or ferric oxide for H2S is adsorbed and oxidized to generate elemental sulfur which is deposited in inner holes or on the surface of active carbon particles, and SO2Is also substantially related to H2S reacting to generate elemental sulfur deposition; or adopting tannin extract method, iron salt method, etc. to treat H2S is absorbed and oxidized to generate elemental sulfur powder which is dispersed in the slurry, and SO2Also substantially absorbed into the slurry, with a minor portion of H2S is reacted to giveTo elemental sulfur, most of which is converted to sulfate; the dry and wet desulphurization can be carried out by adding 3000mg/m of process gas3H of (A) to (B)2S treatment to e.g. 10mg/m3Below, to 5 mg/m3Hereinafter, SO2The content can also reach the emission standard, and the treatment of the type remains H2The S method has the advantages that the sulfur yield is high, but after the activated carbon desulfurizer of the dry method penetrates through the activated carbon desulfurizer, the adsorbed and deposited elemental sulfur needs to be blown down by thermal regeneration and condensed and collected, the desulfurizer is relatively troublesome to regenerate, the problems of safety, sanitation, the direction and treatment of the waste desulfurizer and the like exist in the agent changing process, the elemental sulfur obtained in the wet method process needs to be separated from the powder slurry, the prepared sulfur contains more impurities, and the quality is generally poor; in conclusion this is done to reduce the concentration of H in the outlet gas of the selective oxidation reactor to a low level2The process of converting S into elemental sulfur and preparing sulfur has complex equipment and high process control requirement, and can be used for selective hydrogenation reduction of SO in the reactor2The conversion rate requirement is higher, and the atmospheric emission can not reach the standard when the process control of the previous process is insufficient, the operation fluctuation is low or the load is low, so that the method has obvious defects.
Disclosure of Invention
In order to overcome the technical defects, the invention provides a sulfur recovery process for treating H-containing acid gas with medium and low concentration2S20-50v% of acid gas, wherein the main equipment comprises a combustion furnace, a first-stage Claus reactor, a second-stage Claus reactor, a selective hydrogenation reduction reactor, a selective oxidation reactor and a circulating absorption unit which are sequentially connected in series along the acid gas flow direction; a waste heat boiler is arranged on the combustion furnace, and a first condenser, a second condenser, a third condenser, a fourth condenser, a fifth heater and a fourth heater are respectively arranged at the front and the back of the Claus reactor, the selective hydrogenation reduction reactor and the selective oxidation reactor; the first condenser to the fifth condenser respectively condense the gaseous sulfur in the process gas into liquid sulfur, and the liquid sulfur flows into a liquid sulfur tank for storage; the first heater, the second heater, the third heater, the fourth heater, the fifth heater, the sixth heater, the fifth heater, the sixth heater, the;
wherein, the upper part of the first-stage Claus reactor is filled with Fe2O3/Al2O3Deoxidization protection type sulfurRecovering catalyst from sulfur, filling TiO in the lower part2Based on catalysts for sulphur recovery or pure TiO2Recovering a catalyst from the sulfur; the deoxidation protection type sulfur recovery catalyst not only has the Claus reaction activity, but also can be used for removing O in the process gas2Through with H2S reacts to generate elemental sulfur which is removed; the TiO is2Based on catalysts for sulphur recovery or pure TiO2Besides the Claus reaction activity, the sulfur recovery catalyst also can be used for recovering COS and CS in the process gas2Near total conversion to elemental sulphur or H2S，COS、CS2The total content is less than or equal to 10mg/m3；
The secondary Claus reactor is filled with sulfur recovery catalyst, and further Claus reaction conversion is carried out under the condition that the temperature is lower than that of the primary Claus reaction, wherein the sulfur recovery catalyst is TiO2Sulfur-based recovery catalyst, TiO2/Al2O3Sulfur recovery catalyst and Al2O3One or two of the sulfur recovery catalysts; h in the process gas at the outlet of the two-stage Claus reactor2S+SO2The content of (A) is less than or equal to 1.5 v%;
selective hydrogenation reduction reactor filled with CoO-MoO3/Al2O3Or CoO-MoO3/ TiO2-Al2O3Selective reduction of SO2Catalyst, using H generated in the furnace2Adding SO2Nearly completely reduced, the main product is elemental sulfur and the byproduct is H2S, elemental sulfur is not reduced to H2S；
Selective oxidation reactor is filled with selective oxidation H2S catalyst, O made up by introducing air before the reactor inlet2H is to be2S is approximately converted completely, is selectively oxidized into elemental sulfur, and the byproduct is a small amount of SO2(ii) a H in the process gas at the outlet of the selective oxidation reactor2S content is less than or equal to 100mg/m3， SO2Content of H2More than five times of S content;
the circulating absorption unit comprises an absorption tower, wherein a filler and/or a spraying and atomizing part for distributing and contacting the process gas and the circulating absorption liquid are arranged in the tower, the pH value of the circulating absorption liquid is 5-10, the operation temperature is 20-50 ℃, the main water source is condensed water of steam contained in the process gas, and the surplus liquid outside the circulating absorption liquid maintaining normal operation is sent to a sewage device for treatment, or sent to a coal-fired boiler flue gas wet desulphurization unit for treatment and used as a supplementary water source, or sent to the coal-fired boiler for use as coal shower water; the circulating absorption liquid is an alkali-containing liquid and/or a calcium-containing liquid, wherein the alkali-containing liquid is a sodium sulfite-containing and/or sodium sulfate solution which maintains the absorption capacity by supplementing sodium hydroxide, sodium carbonate or sodium bicarbonate, and the calcium-containing liquid is a calcium sulfite-containing and/or calcium sulfate-containing slurry which maintains the absorption capacity by supplementing calcium oxide, calcium hydroxide and ultrafine calcium carbonate; when the circulating absorption unit adopts calcium-containing liquid, a sixth condenser is arranged at a process gas inlet of the absorption tower, the process gas is cooled to 20-50 ℃ through the sixth condenser, part of steam is condensed into water, sulfur droplets and powder particles contained in the water are collected to form feed liquid containing sulfur powder, the feed liquid is separated into sulfur powder slurry and then enters the absorption tower or an auxiliary circulating absorption liquid storage tank of the absorption tower, and calcium oxide, calcium hydroxide and superfine calcium carbonate are added for circulating absorption;
the sulfur recovery process comprises the following steps:
1) mixing acid gas with required amount of air and/or oxygen-enriched air, then feeding the mixture into a combustion furnace for combustion, controlling the temperature of the combustion furnace at 1050-;
2) heating the process gas from the top of the first condenser to the required temperature of 200-2Hydrolysis of (2); controlling the temperature of the inlet gas of the reactor to make the lower part of the catalyst bed layer in the reactor reach COS and CS2Temperature of full hydrolysis of, wherein TiO2The temperature of the catalyst is 320-350 ℃ when the sulfur-based catalyst is recovered, and pure TiO is2300 ℃ and 350 ℃ when the sulfur is recovered; the outlet process gas enters a second condenser to be cooled to 130-160 ℃, so that the generated elemental sulfur is separated from the process gas and then enters a liquid sulfur tank;
3) heating the process gas from the top of the second condenser to 230 ℃, then feeding the process gas into a secondary Claus reactor for Claus reaction to further generate elemental sulfur, feeding the outlet process gas into a third condenser for cooling to 160 ℃ to separate the generated elemental sulfur from the process gas, and feeding the separated elemental sulfur into a liquid sulfur tank;
4) heating the process gas from the top of the third condenser to 200-220 ℃, and introducing the heated process gas into a selective reduction reactor to obtain SO2Selectively reducing the sulfur into elemental sulfur; the process gas from the selective reduction reactor enters a fourth condenser to be cooled to 130-150 ℃, and the generated elemental sulfur is separated from the process gas and then enters a liquid sulfur tank;
5) adding required amount of air into the process gas from the top of the fourth condenser, uniformly mixing, heating to 200-230 ℃, introducing into a selective oxidation reactor, and allowing the temperature of the lower part of a catalyst bed to reach 220-280 ℃, wherein H is2S is selectively oxidized into elemental sulfur, and the by-product is SO2(ii) a The process gas from the selective oxidation reactor enters a fifth condenser to be cooled to 120-140 ℃, the generated elemental sulfur is separated from the process gas and then enters a liquid sulfur tank, and the process gas is treated by a circulating absorption unit after being trapped by an optional liquid sulfur trap and flowing into the liquid sulfur tank;
6) the process gas from the top of the fifth condenser or the liquid sulfur catcher enters the circulating absorption unit for treatment and then is exhausted through a chimney; when the circulating absorption unit adopts alkali liquor, the temperature of the process gas is reduced, and part of steam is condensed into water, sulfur fog drops, powder particles and SO contained in the process gas2、H2The trapping of S is realized by circulating spraying or atomizing absorption of alkali liquor, the temperature of the alkali liquor is controlled by circulating cooling water, and sulfur powder slurry is separated in the circulation process of the alkali liquor, or the surplus liquid is separated before being sent to a sewage device for treatment or sent to a coal-fired boiler flue gas wet desulphurization unit for treatment; when the circulating absorption unit adopts calcium-containing liquid, the process gas is cooled to 20-50 ℃ by the sixth condenser, and the obtained sulfur powder slurry is separated from the steam condensate containing the sulfur powder and then enters the circulating absorption tower.
In the sulfur recovery process, the first-stage Claus reactor, the second-stage Claus reactor, the selective hydrogenation reduction reactor and the selective oxidation reactor are preferably adiabatic reactors, and the temperature of the middle lower part of a catalyst bed layer reaches the required reaction temperature by controlling the content and the temperature of main reactants in inlet gas and utilizing the exothermic temperature rise of the reaction.
In the sulfur recovery process of the present invention, the SO at the inlet of the primary Claus reactor should be properly controlled2、H2S concentration, the temperature rise of the catalyst bed layer of the primary Claus reactor reaches 80-100 ℃, the temperature of the inlet gas of the reactor is controlled at 250 ℃ as 210-2At a temperature sufficient to hydrolyze and convert, in which case the reaction is carried out at TiO2The temperature of the sulfur-based recovery catalyst is 320-350 ℃ in pure TiO2The sulfur-based recovery catalyst is 300-350 ℃, and the COS and CS in the outlet gas of the primary Claus reactor2The total content can reach less than or equal to 10mg/m3This is a key aspect of the process because such high catalyst bed temperatures are not easily achieved in the post-process and conditions are available that can be converted to elemental sulfur; some can hydrolyze COS and CS at lower temperature such as 250 deg.C2Including TiO-containing catalysts modified by oxides or salts of, for example, alkaline earth metals, transition metals, rare earth metals2Catalyst for hydrolyzing COS and CS2Can be as active and as precise as required, but generally have a much shorter lifetime than the TiO used in the present invention2Sulfur-based recovery catalyst, pure TiO2Recovering a catalyst from the sulfur; the TiO is2Based on catalysts for sulfur recovery, containing TiO2More than 85m percent, the balance being calcium sulfate binder, the surface area being 100-130m2G, pore volume 0.20-0.35 ml/g; the pure TiO2Catalyst containing TiO for recovering sulfur2More than 99m%, surface area of 120-2Per gram, pore volume 0.3-0.5 ml/gram.
In the sulfur recovery process of the invention, the selective oxidation of H2S catalyst comprising Fe2O3/SiO2Or H modified by oxides of alkaline earth metals, rare earth metals, transition metals2S selective oxidation catalyst of Fe2O33-10m%, alkaline earth metal oxide such as CaO 0-3m%,Rare earth metal oxides such as La2O3、CeO2Transition metal oxides such as Cr2O3And/or V2O53-7 m%; the catalyst has average pore diameter of above 30nm, preferably above 35nm, and surface area of 40-60m2The advantages of the catalyst are that liquid sulfur is not condensed to block pores or liquid sulfur is less condensed to block pores in smaller diameter pores at lower bed temperature, thereby ensuring that the activity and reaction degree of the catalyst meet the requirements.
In the sulfur recovery process, the selective oxidation reactor can adopt an adiabatic reactor, and the low H content in the inlet gas is controlled2S content is 0.5-1.1 v% and slightly higher temperature is 200-2S is close to complete conversion, and not only elemental sulfur is generated, but also a small amount of SO which is easy to absorb and treat in subsequent circulating alkali liquor to reach the standard is generated2At the outlet of the reaction gas O2The catalyst has stable performance and the service life is more than 5 years under the condition that the content is less than 1 v%. The usage of the catalyst and the reactor in the prior art adopts proper low inlet temperature, controls the bed temperature at 200 ℃ and 220 ℃ and controls SO2Under the precondition of the generated amount, 90-95% of H is used2S is converted to mainly generate elemental sulfur and SO2Small amount of generated gas H2The concentration of S is far higher than that of SO2The subsequent units are mainly in the adsorption treatment of H with active carbon as desulfurizing agent2S or H in slurry2The method of the active carbon desulfurizer has the defects of complex operation of unloading waste agent and loading new agent when frequent thermal regeneration and scrapping are needed, the problems of shutdown and replacement of the agent and solid waste exist, and H is oxidized into sulfur in slurry2The method for oxidizing S into sulfur has the defect that the quality of the sulfur is low. H when the hydrogen sulfide content of the inlet process gas is less than 0.5v% by selective oxidation2Residual content of S and SO formed2The content of (b) is more easily controlled to the desired range.
In the sulfur recovery process, the circulating absorption unit adopts calciumIn the liquid process, a conventional shell-and-tube heat exchanger, particularly a shell-and-tube heat exchanger with fins can be adopted as the sixth condenser arranged at the process gas outlet of the fifth condenser and the process gas inlet of the calcium liquid circulating absorption unit, the process gas flows through the shell side, and the cooling water flows through the tube side; cooling to 10-50 deg.C, condensing most of steam in the process gas into water on the heat exchange surface, condensing sulfur droplets and sulfur steam carried by the process gas into sulfur powder, collecting the sulfur powder in condensate water, and collecting part of SO in the process gas with the condensate water2、H2S is dissolved and trapped, gas in the heat exchanger enters from bottom to top, the cooling water pipe is integrally from top to bottom, sulfur powder is basically trapped at the middle lower part of the cooling water pipe and at a position where more condensed water exists, the sulfur powder enters the condensed water as much as possible to form slurry and flows out of the heat exchanger, and the sulfur powder is deposited on the surface of the cooling water pipe at the upper part as little as possible to keep the effect of the heat exchanger; the plane of the fin outside the cooling water pipe is preferably arranged in the vertical direction, so that the deposition and condensation of sulfur powder on the surface of the fin are reduced. The heat exchanger can switch the cooling water into superheated steam with the temperature of 250 ℃ on the tube pass when the efficiency is reduced so as to melt, evaporate and remove the sulfur deposited on the heat exchange surface, and the subsequent alkali liquor circulation absorption can temporarily play the role of the heat exchanger. The sixth condenser can also have a structure other than a shell-and-tube heat exchanger, such as the sulfur-containing powder and SO2、H2The condensate of S is used as circulating liquid to realize gas-liquid contact, process gas cooling, sulfur capture and partial SO by spraying and/or atomizing2、H2S is dissolved and absorbed, the condensate is controlled to be at a proper low temperature by cooling water through a liquid-liquid heat exchanger, and the condensing method has the advantages of small loss of process gas pressure head and small influence of sulfur deposition on the condensing effect.
In the sulfur recovery process, the separation of the condensate containing the sulfur powder and the sulfur powder in the alkali-containing solution can be carried out by cyclone sedimentation or natural sedimentation to obtain sulfur powder slurry with higher sulfur powder content; further filtering and separating, or concentrating and accumulating, pressurizing and heating with steam to melt and stratify sulfur powder contained therein, and delivering liquid sulfur to a liquid sulfur tank. Because the concentration of sodium sulfate and sodium sulfite in the alkali-containing solution for trapping sulfur powder is low (less than 3m%, generally less than 2 m%), the sixth condenser condensesThe liquid contains almost no sulfate and sulfite, and contains no solid components except sulfur powder, so that the sulfur powder and separated sulfur powder slurry contain less impurities, are clean, and have purity far higher than that of wet oxidation absorption H containing tannin extract, iron oxyhydroxide and other iron salt components2S to obtain sulfur powder slurry or sulfur.
In the sulfur recovery process, the circulating absorption liquid maintains the rich residual liquid containing sodium sulfate and sodium sulfite or the rich slurry containing calcium sulfate and calcium sulfite outside the normal operation, and the rich residual liquid is sent to a sewage device for treatment, or sent to a coal-fired boiler flue gas wet desulphurization unit for treatment and used as a supplementary water source and raw materials, or sent to a coal-fired boiler for being used as coal shower, wherein the sewage device and the coal-fired boiler flue gas treatment device have more perfect facility conditions and higher management control level, the sulfate-containing solution and the sulfite solution or the slurry of the separated sulfur powder are easy to be treated to reach the standard for discharge or recycling, and the requirement of the slurry as the coal shower is more relaxed. The sewage device and the coal-fired boiler flue gas treatment device have the advantages of perfect facility conditions, high management and control level and easy treatment of sulfate, sulfite solution or slurry containing the separated sulfur powder to the standard discharge or recycling level. Wherein, the mainstream process of the wet desulphurization of the flue gas of the coal-fired boiler is a calcium carbonate-calcium sulfate method, and slurry containing calcium carbonate is sprayed or atomized to absorb SO contained in the flue gas2Generating calcium sulfite, or wet desulphurization by a sodium-calcium double-alkali method, and absorbing SO by sodium hydroxide and/or soda ash2Adding lime to generate calcium sulfite and regenerating alkali; the obtained calcium sulfite is oxidized into calcium sulfate by blown air, and then the calcium sulfate is separated and utilized. The surplus liquid containing sodium sulfate and sodium sulfite is preferably sent to the wet desulphurization by a sodium-calcium double alkali method, and the surplus slurry containing calcium sulfate and calcium sulfite can be sent to any one of the wet desulphurization by a calcium carbonate-calcium sulfate method or a sodium-calcium double alkali method. The surplus liquid containing sodium sulfate and sodium sulfite and the surplus slurry containing calcium sulfate and calcium sulfite have simple components, almost do not contain organic components, have small quantity, and are easy to treat in sewage devices and coal-fired boiler flue gas desulfurization devices because the contained water is the cold of steam in the process gasThe alkali and calcium raw materials added in the condensed water are simple and nontoxic.
In the sulfur recovery process, because the surplus absorption liquid is sent to a sewage device for treatment, or sent to a coal-fired boiler flue gas wet desulphurization unit for treatment and used as a water supply, or sent to the coal-fired boiler for coal spraying, the dosage of alkali or calcium can be properly relaxed, i.e. higher dosage or concentration is adopted, so that the circulating absorption liquid has higher absorption capacity, for example, the pH value of alkali liquor can be higher, and the priority is ensured for H2S、SO2The absorption capacity of the device ensures that the concentration of the atmospheric emission reaches the standard or is lower, but is not higher than the utilization rate of alkali and calcium; the method meets the requirements of users or downstream users without excessively counting whether the crystallization condition of the calcium sulfate reaches the standard, and because the amount of the absorption liquid, the concentration of alkali and calcium contained in the absorption liquid are usually far lower than the liquid amount and the concentration of the absorption liquid during the wet desulphurization of the flue gas of the coal-fired boiler, the absorption liquid can not cause obvious influence on the absorption liquid.
The sulfur recovery process utilizes the process gas H2The condensed water of the steam byproduct generated in S oxidation sulfur production is used as a water source of the circulating absorption unit, and special supplement and control of water are not needed. Different H2The process gas with S content acid gas contains condensate amounts of steam at different condensing temperatures as listed in table 1 below. Calculating conditions: h in acid gas2S reacts with the required amount of air to be converted into sulfur, and the air is not excessive; the saturated vapor pressure of water is 12kPa at 50 ℃ and 7.4kPa at 40 ℃; the acid gas does not contain components such as hydrocarbon, ammonia and the like which can react with air to generate water; when the furnace is used with oxygen-enriched air or oxygen-enriched air + air, the amount of condensed water per unit volume of process gas is greater than when air is used.
TABLE 1 number of condensates of steam contained in the process gas at different condensation temperatures
In the sulfur recovery process, SO of the process gas at the outlet of the selective oxidation reactor or the process gas at the inlet of the circulating absorption unit2Easy to control to 1000 mg/m3The content of the active carbon is controlled within the range,can be controlled to 600 mg/m3Internal, especially when acid gas conditions fluctuate less; according to the amount of the condensed water listed in Table 1, the concentrations of sulfate and sulfite in the circulating absorption liquid are easily controlled within 2m%, even within 1m%, and even the slurry containing calcium sulfate and calcium sulfite is easily transported for a long distance; fog drops discharged from the top end of the chimney and entering the chimney and the atmosphere contain less salt, the corrosion to the chimney is much lighter, colored smoke plume is not easy to generate when the smoke drops are discharged from the top end of the chimney, white powder particles are not easy to float off on the ground near the chimney when the wind speed is low, and the concentration of sulfate and sulfite in the circulating absorption liquid is far lower than that in SO treated by the prior alkali method, calcium method and ammonia method technologies2The circulating absorption liquid of (2) has a high concentration level of sulfite and sulfate of more than 10 m%. The existing alkali method, calcium method and ammonia method technologies for treating SO2In the circulating absorption liquid, because the sulfite and the sulfate are contained in the circulating absorption liquid, the general demister has poor trapping capacity on salt-containing liquid drops with the diameter of less than 2.5 mu m, process gas containing sulfite and sulfate liquid drops with high concentration enters a chimney and the atmosphere and corrodes the chimney, visible smoke plume is easily generated when the gas is exhausted from the top end of the chimney, and white particles are easily drifted off on the ground near the chimney at low wind speed. H of process gas at outlet of selective oxidation reactor or process gas at inlet of circulating absorption unit2S, since its content is much lower than SO2The content is easy to be absorbed and processed to the required 10mg/m3The following contents; h2The product of S in the absorption liquid is also easily converted into harmless substances such as sulfates during the treatment or use of the rich absorption liquid.
In the sulfur recovery process, the process gas after cyclic absorption can be heated to 75 ℃ or above through heat exchange and then enters the chimney for evacuation, steam in the process gas is unsaturated, condensate is not generated in the chimney basically, corrosion to the chimney is reduced, the service life is prolonged, and no smoke plume can be seen at the top end of the chimney basically.
In the sulfur recovery process, a small amount of process gas after the cyclic absorption treatment can be used as purge gas to purify a liquid sulfur tank and liquid sulfur and returns to an acid gas storage tank in front of a combustion furnace, so that H contained in the liquid sulfur is removed2And S and the like are recycled.
The first heater, the second heater, the third heater, the fourth heater, the fifth condenser and the fifth condenser are combined together, and the heating and heat exchanging modes can be combined together.
The process gas outlet section in the fifth condenser can be provided with one or more layers of baffle members or silk screens and fillers made of stainless steel or PTFE materials, and liquid sulfur droplets are collected by falling back by utilizing the self gravity of the liquid sulfur. And a liquid sulfur mist catcher can be optionally arranged behind the second condenser, the mist catcher collects the liquid sulfur droplets in the gas, the liquid sulfur droplets fall back by utilizing the self gravity of the liquid sulfur and are collected into the liquid sulfur, and a mist catching part of the liquid sulfur mist catcher is a baffle made of stainless steel or PTFE material or a wire mesh or filler.
The sulfur recovery process of the invention does not need an incinerator, and has no problems of fuel consumption, supply and cost.
Drawings
FIG. 1 is a schematic process flow diagram of the acid gas sulfur recovery process of the present invention.
The equipment numbers in fig. 1 are in sequence: 1 combustion furnace, 2 waste heat boiler, 3 first condenser, 4 second condenser, 5 third condenser, 6 fourth condenser, 7 fifth condenser, 8 sixth condenser, 9 first heater, 10 second heater, 11 third heater, 12 fourth heater, 13 first-stage Claus reactor, 14 second-stage Claus reactor, 15 selective hydrogenation reduction reactor, 16 selective oxidation reactor, 17 absorption liquid tower, 18 sulfur slurry knockout drum, 19 circulating pump, 20 liquid sulfur trough, 21 chimney, 22 adsorbent tower.
Detailed Description
In a set of 6000 ton/year scale acid gas sulfur recovery device, some process parameter experiments are carried out, and absorption treatment experiments are carried out on the process gas at the outlet of a fifth condenser behind a selective oxidation reactor, so as to explain the process of the invention, but not limit the process of the invention.
The sulfur recovery device comprises a combustion furnace, a first-stage Claus reactor, a second-stage Claus reactor and a selective hydrogenation reduction reactor which are sequentially connected in series along the acid gas flow directionThe selective oxidation reactor and the circulating absorption unit; a waste heat boiler is arranged on the combustion furnace, and a first condenser, a second condenser, a third condenser, a fourth condenser, a fifth heater and a fourth heater are respectively arranged at the front and the back of the Claus reactor, the selective hydrogenation reduction reactor and the selective oxidation reactor; the first condenser to the fifth condenser respectively condense the gaseous sulfur in the process gas into liquid sulfur, and the liquid sulfur flows into a liquid sulfur tank for storage; the first heater, the second heater, the third heater, the fourth heater, the fifth heater, the sixth heater, the fifth heater, the sixth heater, the; wherein, the upper part of the first-stage Claus reactor is filled with Fe2O3/Al2O3Deoxidizing and protecting type sulfur recovering catalyst with TiO filled in its lower part2Recovering catalyst based on sulfur; filling TiO in secondary Claus reactor2Recovering catalyst based on sulfur; selective hydrogenation reduction reactor filled with CoO-MoO3/Al2O3Selective reduction of SO2A catalyst; selective oxidation reactor charging with Fe2O3-CeO2-Cr2O3/SiO2Selective oxidation of H2And (4) an S catalyst.
In the normal process of the sulfur recovery device, the process gas at the outlet of the fifth condenser behind the selective oxidation reactor is treated by an active carbon desulfurizer tower and then discharged by a chimney of 90 m. The acid gas treated during the experiment contained H2S30-40v%。
In order to verify the process of the invention, a small-sized sixth condenser and a circulating absorption unit experimental device are arranged behind the fifth condenser, and the process gas is fed by 1.0-1.1m3The flow rate per minute (measured after the sixth condenser) is introduced into the sixth condenser and the circulating absorption unit through a fifth condenser outlet pipeline branch pipe; the circulating absorption unit comprises a transparent plastic absorption tower and an absorption liquid circulating pump, the bottom of the absorption tower is also used as an absorption liquid storage tank, an atomizing nozzle is arranged at the top in the absorption tower, a hollow cylinder part at the middle upper part of the absorption tower is an absorption liquid atomizing absorption space, and the atomizing nozzle can effectively distribute and fill the absorption liquid in the atomizing absorption space to play a role in full absorption; the sixth condenser cools to 40 ℃ through circulating water, condensate discharged from a liquid outlet at the bottom of the sixth condenser is settled and collected by a transparent plastic cylinder, and then flows to the bottom of the absorption towerThe air outlet is connected with the middle lower part of the absorption tower to send the process gas into the absorption tower; the top of the absorption tower is provided with an exhaust port which is connected with a NaOH/activated carbon tower, and the process gas is discharged into the on-site environment after being treated. Respectively using NaHCO with the concentration of 1m%3Solution, superfine CaCO3The slurry serves as an absorption liquid.
The main process parameters of the first stage of the experiment include:
the temperature of a combustion furnace is about 1150 ℃, the temperature of the process gas after the waste heat boiler is 350 ℃, the temperature of the process gas at the outlet of the first condenser is 170 ℃, and the temperature of H is H2S4v%， SO22.5v%，COS+CS20.5v%；
The temperature of the process gas at the outlet of the first heater is 239 ℃, the temperature of the lower part of the catalyst bed layer of the first-stage Claus reactor is 325 ℃, the temperature of the process gas at the outlet of the second condenser is 150 ℃, and the temperature of H is H2S 1.4v%，SO20.7v%，COS+CS2≤5mg/m3；
The temperature of the process gas at the outlet of the second heater is 210 ℃, the temperature of the lower part of the catalyst bed layer of the second-stage Claus reactor is 236 ℃, the temperature of the process gas at the outlet of the third condenser is 140 ℃, and the temperature of H is H2S0.6v%，SO20.3v%；
The temperature of the process gas at the outlet of the third heater is 220 ℃, the temperature of the lower part of the catalyst bed layer of the selective hydrogenation reduction reactor is 240 ℃, the temperature of the process gas at the outlet of the fourth condenser is 140 ℃, and the temperature of H is H2S0.5v%，SO2≤20mg/m3；
Adding required amount of air into the process gas at the outlet of the fourth condenser, uniformly mixing the air and the process gas in the fourth heater, wherein the temperature of the process gas at the outlet is 215 ℃, the temperature of the lower part of a catalyst bed layer of the selective oxidation reactor is 242 ℃, the temperature of the process gas at the outlet of the fourth condenser is 135 ℃, and H is2S60-90mg/m3，SO2800-1000mg/m3，O20.4-0.8v%， CO2About 30v%, the balance being steam and N2；
The outlet gas temperature of the sixth condenser is 40 ℃, and the condensate amount of a bottom liquid outlet is about 125-;
the absorption liquid of the absorption tower adopts 1m percent NaHCO3In the case of the solution, the initial pH is about 8, and the outlet gas H of the absorption tower2S≤2mg/m3，SO2≤10mg/m3(ii) a Calculating NaHCO according to the amount of treated gas and the amount of absorbed liquid3When 80% is consumed, the outlet gas H of the absorption tower2S≤5mg/m3，SO2≤20mg/m3，COS+CS2≤6mg/m3；
The absorption liquid of the absorption tower adopts 1m percent of CaCO3When the slurry is in use, the initial pH value is about 5.5, and the outlet gas H of the absorption tower2S≤5mg/m3，SO2≤20mg/m3(ii) a CaCO calculation from the amount of gas treated and the amount of liquid absorbed3When 60% is consumed, the outlet gas H of the absorption tower2S≤8mg/m3，SO2≤30mg/m3，COS+CS2≤6mg/m3。
The main process parameters of the second stage of the experiment include:
the temperature of a combustion furnace is 1180 ℃, the temperature of the process gas after the waste heat boiler is 350 ℃, the temperature of the process gas at the outlet of the first condenser is 170 ℃, and the temperature of H is about2S4.5v%，SO22.5v%，COS+CS20.5v%；
The temperature of the process gas at the outlet of the first heater is 230 ℃, the temperature of the lower part of the catalyst bed layer of the first-stage Claus reactor is 325 ℃, the temperature of the process gas at the outlet of the second condenser is 150 ℃, and the temperature of H is H2S 1.6v%，SO20.7v%，COS+CS2≤5mg/m3；
The temperature of the process gas at the outlet of the second heater is 205 ℃, the temperature of the lower part of the catalyst bed layer of the second-stage Claus reactor is 230 ℃, the temperature of the process gas at the outlet of the third condenser is 140 ℃, and the temperature of H is H2S0.7v%，SO20.2v%；
The temperature of the process gas at the outlet of the third heater is 220 ℃, the temperature of the lower part of the catalyst bed layer of the selective hydrogenation reduction reactor is 245 ℃, the temperature of the process gas at the outlet of the fourth condenser is 140 ℃, and the temperature of H is2S0.6v%，SO2≤20mg/m3；
Adding required amount of air into the process gas at the outlet of the fourth condenser, uniformly mixing the air and the process gas in the fourth heater, wherein the temperature of the process gas at the outlet is 225 ℃, the temperature of the lower part of a catalyst bed layer of the selective oxidation reactor is 260 ℃, the temperature of the process gas at the outlet of the fourth condenser is 135 ℃, and H is2S30-50mg/m3，SO21000-1200mg/m3，O20.8-1.3v%，CO2About 45v%, the remainder being N2；
The outlet gas temperature of the sixth condenser is 40 ℃, and the condensate amount of a bottom liquid outlet is about 125-;
the absorption liquid of the absorption tower adopts 1m percent NaHCO3In the case of the solution, the initial pH is about 8, and the outlet gas H of the absorption tower2S≤2mg/m3，SO2≤10mg/m3，COS+CS2≤4mg/m3(ii) a Calculating NaHCO according to the amount of treated gas and the amount of absorbed liquid3When 80% is consumed, the outlet gas H of the absorption tower2S≤5mg/m3，SO2≤25mg/m3，COS+CS2≤6mg/m3；
The absorption liquid of the absorption tower adopts 1m percent of CaCO3When the slurry is in use, the initial pH value is about 5.5, and the outlet gas H of the absorption tower2S≤3mg/m3，SO2≤30mg/m3，COS+CS2≤6mg/m3(ii) a CaCO calculation from the amount of gas treated and the amount of liquid absorbed3When 60% is consumed, the outlet gas H of the absorption tower2S≤6mg/m3，SO2≤35mg/m3，COS+CS2≤6mg/m3。
In the above two-stage experiments, the condensate discharged from the liquid outlet at the bottom of the sixth condenser is collected and settled in the transparent plastic cylinder, the sulfur slurry obtained at the bottom layer has yellow color and is easy to settle and filter, the supernatant is clear, and the sulfur obtained by filtering has purity higher than 99.5m% after being simply washed and dried, and has purer and more positive color. The sulfur slurry has good quality, can be pumped and pressurized by a pump when a certain amount of sulfur slurry is accumulated, is melted by low-pressure steam, and the separated liquid sulfur directly enters a liquid sulfur trough for recovery.
The 1m% NaHCO is treated by the sewage treatment device and coal-fired boiler device personnel of the company380% of CaCO is consumed by the solution3The absorption surplus liquid containing sulfate, sulfite and a small amount of sulfide salt when the slurry consumes 60 percent is subjected to detailed detection of inorganic components and organic components, the inorganic components are simple and low in content, the inorganic components hardly contain organic components, and the sulfur is relative to the treatment amount or required amount of a sewage treatment device, a coal-fired boiler flue gas wet desulphurization unit or coal shower waterWhen the sulfur recovery process is used in an industrial device, the liquid discharge amount is small, so that the sulfur recovery process can be sent to a sewage device for treatment and discharge, and also can be sent to a coal-fired boiler flue gas wet desulphurization unit for utilization and used as coal water.
The sulfur recovery process of the invention is used in the outlet gas of the absorption tower in an industrial device, namely SO2The content meets the requirement of ultra-low emission, H2S、COS、CS2The content of the odor substances is extremely low, the emission requirement is met, and the odor substances can be exhausted through a chimney.
Claims (9)
1. A sulfur recovery process for treating H-containing gas with middle-low concentration of acid gas2S20-50v% of acid gas, wherein the main equipment comprises a combustion furnace, a first-stage Claus reactor, a second-stage Claus reactor, a selective hydrogenation reduction reactor, a selective oxidation reactor and a circulating absorption unit which are sequentially connected in series along the acid gas flow direction; a waste heat boiler is arranged on the combustion furnace, and a first condenser, a second condenser, a third condenser, a fourth condenser, a fifth heater and a fourth heater are respectively arranged at the front and the back of the Claus reactor, the selective hydrogenation reduction reactor and the selective oxidation reactor; the first condenser to the fifth condenser respectively condense the gaseous sulfur in the process gas into liquid sulfur, and the liquid sulfur flows into a liquid sulfur tank for storage; the first heater, the second heater, the third heater, the fourth heater, the fifth heater, the sixth heater, the fifth heater, the sixth heater, the;
wherein, the upper part of the first-stage Claus reactor is filled with Fe2O3/Al2O3Deoxidizing and protecting type sulfur recovering catalyst with TiO filled in its lower part2Based on catalysts for sulphur recovery or pure TiO2Recovering a catalyst from the sulfur; the deoxidation protection type sulfur recovery catalyst not only has the Claus reaction activity, but also can be used for removing O in the process gas2Through with H2S reacts to generate elemental sulfur which is removed; the TiO is2Based on catalysts for sulphur recovery or pure TiO2Besides the Claus reaction activity, the sulfur recovery catalyst also can be used for recovering COS and CS in the process gas2Near total conversion to elemental sulphur or H2S，COS、CS2The total content is less than or equal to 10mg/m3；
Two-stage Claus reactorFilling a sulfur recovery catalyst, and performing further Claus reaction conversion at a temperature lower than the first-stage Claus reaction temperature, wherein the sulfur recovery catalyst is TiO2Sulfur-based recovery catalyst, TiO2/Al2O3Sulfur recovery catalyst and Al2O3One or two of the sulfur recovery catalysts; h in the process gas at the outlet of the two-stage Claus reactor2S+SO2The content of (A) is less than or equal to 1.5 v%;
selective hydrogenation reduction reactor filled with CoO-MoO3/Al2O3Or CoO-MoO3/ TiO2-Al2O3Selective reduction of SO2Catalyst, using H generated in the furnace2Adding SO2Nearly completely reducing, and the main product is elemental sulfur;
selective oxidation reactor is filled with selective oxidation H2S catalyst, O made up by introducing air before the reactor inlet2H is to be2S is approximately converted completely, is selectively oxidized into elemental sulfur, and the byproduct is a small amount of SO2(ii) a H in the process gas at the outlet of the selective oxidation reactor2S content is less than or equal to 100mg/m3，SO2Content of H2More than five times of S content; the selective oxidation of H2S catalyst is SiO2As a carrier, Fe2O33-10m%，CaO 0-3m%，La2O3+CeO2+Cr2O3+V2O53-7 m%; the average pore diameter of the catalyst is more than 30nm, and the surface area is 40-60m2G, pore volume 0.5-0.6 ml/g;
the circulating absorption unit comprises an absorption tower, wherein a filler and/or a spraying and atomizing part for distributing and contacting the process gas and the circulating absorption liquid are arranged in the tower, the pH value of the circulating absorption liquid is 5-10, the operation temperature is 20-50 ℃, the main water source is condensed water of steam contained in the process gas, and the surplus liquid outside the circulating absorption liquid maintaining normal operation is sent to a sewage device for treatment, or sent to a coal-fired boiler flue gas wet desulphurization unit for treatment and used as a supplementary water source, or sent to the coal-fired boiler for use as coal shower water; the circulating absorption liquid is an alkali-containing liquid and/or a calcium-containing liquid, wherein the alkali-containing liquid is a sodium sulfite-containing and/or sodium sulfate solution which maintains the absorption capacity by supplementing sodium hydroxide, sodium carbonate or sodium bicarbonate, and the calcium-containing liquid is a calcium sulfite-containing and/or calcium sulfate-containing slurry which maintains the absorption capacity by supplementing calcium oxide, calcium hydroxide and ultrafine calcium carbonate; when the circulating absorption unit adopts calcium-containing liquid, a sixth condenser is arranged at a process gas inlet of the absorption tower, the process gas is cooled to 20-50 ℃ through the sixth condenser, part of steam is condensed into water, sulfur droplets and powder particles contained in the water are collected to form feed liquid containing sulfur powder, the feed liquid is separated into sulfur powder slurry and then enters the absorption tower or an auxiliary circulating absorption liquid storage tank of the absorption tower, and calcium oxide, calcium hydroxide and superfine calcium carbonate are added for circulating absorption;
the sulfur recovery process comprises the following steps:
1) mixing acid gas with required amount of air and/or oxygen-enriched air, then feeding the mixture into a combustion furnace for combustion, controlling the temperature of the combustion furnace at 1050-;
2) the process gas coming out from the top of the first condenser is heated to the required temperature of 210-2Hydrolysis of (2); controlling the H of the reactor inlet gas2S、SO2The content and temperature of the catalyst are such that the lower part of the catalyst bed in the reactor reaches COS and CS2Temperature of full hydrolysis of, wherein TiO2The temperature of the catalyst is 320-350 ℃ when the sulfur-based catalyst is recovered, and pure TiO is2300 ℃ and 350 ℃ when the sulfur is recovered; the outlet process gas enters a second condenser to be cooled to 130-160 ℃, so that the generated elemental sulfur is separated from the process gas and then enters a liquid sulfur tank;
3) heating the process gas from the top of the second condenser to 230 ℃ and then feeding the process gas into a secondary Claus reactor; the process gas from the secondary Claus reactor enters a third condenser to be cooled to 130-160 ℃, so that the generated elemental sulfur is separated from the process gas and then enters a liquid sulfur tank;
4) heating the process gas from the top of the third condenser to 200-220 ℃, and entering the selective reduction reactor; the process gas from the selective reduction reactor enters a fourth condenser to be cooled to 130-150 ℃, and the generated elemental sulfur is separated from the process gas and then enters a liquid sulfur tank;
5) adding required amount of air into the process gas from the top of the fourth condenser, uniformly mixing, heating to the temperature of 200-230 ℃, and then feeding into a selective oxidation reactor, wherein the temperature of the lower part of a catalyst bed layer reaches 220-280 ℃; the process gas from the selective oxidation reactor enters a fifth condenser to be cooled to 120-140 ℃, the generated elemental sulfur is separated from the process gas and then enters a liquid sulfur tank, and the process gas is treated by a circulating absorption unit after being trapped by an optional liquid sulfur trap and flowing into the liquid sulfur tank;
6) the process gas from the top of the fifth condenser or the liquid sulfur catcher enters the circulating absorption unit for treatment and then is exhausted through a chimney; when the circulating absorption unit adopts alkali liquor, the temperature of the process gas is reduced, and part of steam is condensed into water, sulfur fog drops, powder particles and SO contained in the process gas2、H2The S is collected by circulating spraying or atomizing absorption of alkali liquor, the temperature of the alkali liquor is controlled by circulating cooling water, and the sulfur powder slurry is separated in the circulation process of the alkali liquor, or the residual liquid is separated before being sent to a sewage device for treatment or sent to a coal-fired boiler flue gas wet desulphurization unit for treatment.
2. The process for sulfur recovery from acid gas of claim 1, wherein the primary claus reactor, the secondary claus reactor, the selective hydrogenation reduction reactor, and the selective oxidation reactor are adiabatic reactors.
3. The process for sulfur recovery from acid gas of claim 1, wherein the primary claus reactor is charged with the catalyst, and wherein the TiO is in the catalyst2Based on catalysts for sulfur recovery, containing TiO2More than 85m percent, the balance being calcium sulfate binder, the surface area being 100-130m2G, pore volume 0.20-0.35 ml/g; the pure TiO2Catalyst containing TiO for recovering sulfur2More than 99m%, surface area of 120-2Per g, pore volume0.3-0.5ml/g。
4. The process for recovering the sulfur from the acid gas according to claim 1, wherein the circulating absorption unit is a sixth condenser arranged when the calcium-containing liquid is adopted, the gas enters from the bottom to the top, and the cooling water pipe is arranged from the top to the bottom as a whole, so that the sulfur powder is captured at the middle lower part and the position with more condensed water of the cooling water pipe to form slurry which flows out of the heat exchanger.
5. The process for recovering the sulfur from the acid gas as claimed in claim 1, wherein the separation of the sulfur powder in the condensate containing the sulfur powder and the alkali-containing solution in the circulating absorption unit is carried out by cyclone sedimentation or natural sedimentation to obtain a sulfur powder slurry with higher content of the sulfur powder; the sulfur powder slurry is further filtered and separated, or after concentration and accumulation, the sulfur is pressurized and heated by steam to melt the sulfur, and after layering, the liquid sulfur is sent to a liquid sulfur tank.
6. The process for recovering sulfur from acid gas according to claim 1, wherein the surplus solution containing sodium sulfate and sodium sulfite, which is obtained after the circulating absorption solution is maintained in normal operation, is sent to the sodium-calcium double alkali wet desulfurization; and (3) sending the surplus slurry containing calcium sulfate and calcium sulfite to a calcium carbonate-calcium sulfate method or a sodium-calcium double-alkali wet desulphurization method.
7. The process for recovering sulfur from acid gas according to claim 1, wherein the amount of the alkali-containing raw material fed or concentrated in the circulating absorption solution is 20% or more higher than the required amount, and the amount of the calcium-containing raw material fed or concentrated is 40% or more higher than the required amount.
8. The process for recovering sulfur from acid gas as defined in claim 1, wherein a small amount of process gas after said cyclic absorption treatment is used as a purge gas to purify a liquid sulfur tank and liquid sulfur and returned to the acid gas storage tank before the combustion furnace; and/or the process gas after the cyclic absorption treatment is heated to more than 75 ℃ through heat exchange and then enters a chimney for evacuation.
9. The process for recovering the sulfur from the acid gas as claimed in claim 1, wherein the first to fourth heaters are realized by medium-high pressure steam, heat conducting oil and fuel combustion and/or are combined with the first to fifth condensers to perform countercurrent heat exchange; and/or a process gas outlet section in the fifth condenser is provided with one or more layers of baffle members or silk screens made of stainless steel or PTFE materials and fillers for trapping liquid sulfur fog drops, and the liquid sulfur is collected as liquid sulfur by falling back by utilizing the self gravity of the liquid sulfur.
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