CN113694940B - Production process of sulfur-free gas hydrogenation catalyst - Google Patents
Production process of sulfur-free gas hydrogenation catalyst Download PDFInfo
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Abstract
The invention discloses a production process of a sulfur-free gas hydrogenation catalyst. Preparation of FeMo/Al by isovolumetric impregnation method 2 O 3 、CoMo/Al 2 O 3 、NiMo/Al 2 O 3 The gas hydrogenation catalyst adopts a limited hydrogen control circulation vulcanization process to presulfide the catalyst outside the reactor, and sulfur-discharging tail gas passes through Cu/C or Cu/Al 2 O 3 H removal 2 And S, emptying, and passivating after sulfur removal is finished. The process has flexible operation, low hydrogen consumption, high utilization rate of vulcanizing agent, short vulcanizing time and good vulcanizing effect. The exhaust emission is less in the whole external presulfiding process, and the exhaust component is simpler than coke oven gas and is easy to purify; cu/C or Cu/Al 2 O 3 The catalyst is used as a gas mercury removal agent after desulfurization, and is green and economical.
Description
Technical Field
The invention relates to a production process of a sulfur-free gas hydrogenation catalyst, belonging to the field of coal chemical industry.
Background
China is a large country for coke production, and a large amount of coke oven gas is produced as a byproduct. The production of methanol/LNG from coke oven gas has good application prospect. Methanol and LNG are produced by using a methanol synthesis catalyst and a methanation catalyst, wherein the active components of the catalyst are Cu and Ni respectively, and the catalyst is easy to react with sulfides to be permanently deactivated. Therefore, the removal of various sulfides in coke oven gas is of great significance.
The sulfur content in the coke oven gas is related to the total sulfur content of the coal charge, and is generally 0.5-1.2 percent (weight) of total sulfur in the dry coal, wherein 20-45 percent is transferred into the coke oven gas, and the hydrogen sulfide accounts for more than 95 percent of the total sulfur content. Besides hydrogen sulfide, coke oven gas also contains various sulfides such as carbonyl sulfide, carbon disulfide, thiophene, mercaptan, thioether and the like. The desulfurization process of coke oven gas is generally to remove hydrogen sulfide through a wet method and an active carbon method, wherein the fine desulfurization process adopts a process of pre-hydrogenation, primary hydrogenation, medium temperature desulfurization, secondary hydrogenation and zinc oxide desulfurization, and the total sulfur in the coarse degassing is removed to be lower than 100ppb so as to protect the copper-nickel catalyst. The active component of the gas hydrogenation catalyst is usually MoO 3 、CoO、NiO、Fe 2 O 3 And the like, only in the vulcanized state, has higher catalytic activity, so that the catalyst is vulcanized before being used. At present, most of the vulcanization technology of the gas hydrogenation catalyst is from the vulcanization operation of the earlier sulfur-tolerant shift catalyst, and is generally carried out by adopting an in-reactor dry vulcanization method, wherein the main reactions are as follows:
MoO 3 +2H 2 S+H 2 =MoS 2 +3H 2 O
9CoO+8H 2 S+H 2 =Co 9 S 8 +9H 2 O
3NiO+2H 2 S+H 2 =Ni 3 S 2 +3H 2 O
Fe 2 O 3 +3H 2 S= Fe 2 S 3 +3H 2 O
therefore, after the methanol/natural gas/glycol manufacturers with coke oven gas are filled with the pre-hydrogenation, primary hydrogenation and secondary hydrogenation catalysts, the catalysts need to be heated, vulcanized, cooled and sulfur removed before being put into use. The problems associated with such conventional hydrogenation catalysts and their use are mainly pointed out as follows.
1. The problem of the catalyst being reduced prior to sulfiding cannot be solved. In-vessel dry curing is typically carried out by adding a curing agent CS 2 Hydrogenolysis to form H required for sulfidation 2 S：
CS 2 +4H 2 =2H 2 S+CH 4
Most of the vulcanization operations require H 2 More than 25 percent, and a plurality of factories are completely vulcanized coke oven gas, H 2 More than 50%, CO content is 7% -10%, and H 2 The initial yield of S is usually less than 1%, and CS is at about 200 DEG C 2 The hydrogenolysis activity is not good, and many sites are filled with CS 2 1-2 hours, H is detected at the inlet of the catalyst 2 S is very low. Such a H-rich 2 Lean in CO H 2 The S-sulfide gas readily reduces the catalyst prior to sulfiding. In addition, the time needed for the vulcanization to reach the bottom from the upper end of the bed layer to the lower layer by layer is longer, the larger the catalyst loading amount is, the lower the vulcanization airspeed is, the smaller the sulfur injection amount is, and the longer the sulfur penetrates through the bed layer. The oxidation state active components of the underlying catalyst not penetrated by sulfur, possibly by H in the coke oven gas 2 The higher the temperature, the easier the reduction, the more exothermic the vulcanization, the higher the temperature rise caused by the vulcanization of the upper catalyst tends to reduce the lower catalyst, the reduced catalyst is difficult to fully vulcanize, and the hydrogenation activity is affected.
2. And the problem of sulfuration waste gas treatment and emission is caused. The sulfuration is intermittent operation, the replacement period of the pre-hydrogenation which is more frequent is half a year, the primary hydrogenation is more than one year, the secondary hydrogenation is two years, and common factories for preparing methanol/natural gas/glycol from coke oven gas do not have a device for specially purifying sulfuration gas. Direct sulfidation of exhaust gasThe emptying emission not only seriously pollutes the environment, but also has high temperature, high flow and high H in the later stage of vulcanization 2 The S-content sulfuration gas also can cause emptying and ignition to generate potential safety hazards, and often the sulfuration process is interrupted, so that sulfuration is insufficient, the service activity of the catalyst is reduced, and the service period is shortened.
3. And the equipment such as a reactor, a pipeline, a valve and the like are polluted. Common in-reactor dry vulcanization inevitably occurs when vulcanization and part of normally produced pipe fittings are shared, and H in vulcanized gas 2 The S content is very high, and the high-temperature strengthening period can reach 10-40 g/m 3 High-concentration high-temperature sulfuration gas is easy to pollute the reactor, the pipeline, the valve and other devices. In particular, secondary hydrogenation, is too close to the plumbing required for ppb levels of sulfur, and can be cumbersome once contaminated.
4. Long start-up time and influence production. The general vulcanization has a heating period, a vulcanization period, a strengthening period and a cooling replacement period, even if the whole vulcanization process and the system entering are smooth, the vulcanization time is at least twenty hours, and if the vulcanization empty speed is low, the catalyst bed layer is overtemperature during vulcanization, and the vulcanization time is longer. Moreover, it may be that the primary hydrogenation and the secondary hydrogenation are difficult to replace without stopping production except the pre-hydrogenation due to economic consideration during design.
With the increasingly stringent environmental protection requirements of the state, on-site vulcanization is increasingly difficult to realize, and some coke oven gas downstream manufacturers are even forced to use hydrogenation catalysts unsulfided and low in efficiency, so that the gas hydrogenation catalysts which are ready to be filled and used are urgently needed. The presulfiding hydrogenation catalysts disclosed in the patents CN201110350766, CN201110350791, CN201310358571 and CN201110350794 generally need to be activated before use, and concentrated heat release and sulfur release during activation are common, and if the presulfiding hydrogenation catalysts are used for gas hydrogenation, the operation difficulty before the entry system is involved in production and the emission problem is not very different from the on-site vulcanization, so that the presulfiding hydrogenation catalysts cannot be used at all.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides a production process of a sulfur-free gas hydrogenation catalyst. Preparation of FeMo/Al by isovolumetric impregnation method 2 O 3 、CoMo/Al 2 O 3 、NiMo/Al 2 O 3 The isogas hydrogenation catalyst is presulfided outside the catalyst by adopting a limited hydrogen control circulation vulcanization process, and the sulfur-discharging tail gas is subjected to H removal by Cu/C or Cu/Al2O3 2 And S, emptying, and passivating after sulfur removal is finished. The low-temperature vulcanizing period of the external presulfiding is provided with three mixing, hydrolyzing and vulcanizing towers which are connected in series, the metered carbon disulfide, water vapor and limited hydrogen are uniformly mixed in the mixing tower and converted into H required by vulcanization through the hydrolyzing tower 2 S, the problem that the catalyst in the vulcanizing tower is reduced before vulcanization is avoided by lean hydrogen distribution operation before the catalyst is not vulcanized and penetrated. Cu/C or Cu/Al 2 O 3 The catalyst is used as a gas mercury removal agent after desulfurization. The produced sulfur-free gas hydrogenation catalyst does not need activation treatment before use, and is ready to use after being filled.
The invention is realized by the following technical scheme:
preparation of FeMo/Al 2 O 3 、CoMo/Al 2 O 3 、NiMo/Al 2 O 3 An isopipe hydrogenation catalyst. Considering that the sulfuration-free gas hydrogenation catalyst has the operations of loading and unloading, the catalyst must have higher strength and better anti-powdering performance. Spherical Al with the strength of 120-165N/particle and the water content of 65-78% is selected 2 O 3 Preparing a solution of iron, cobalt, nickel and molybdenum salts required by the carrier, regulating the pH value of the impregnating solution to 5.5-6.8 by phosphoric acid, carrying out one-step loading in an equal volume, controlling the impregnating time to be 1 hour and 40 minutes due to the fact that the impregnating time is short and the loading is uneven and the impregnating time is too long, and baking at the temperature of 100-120 ℃ for 2-3 hours and at the temperature of 350-550 ℃ for 2.5-4 hours.
The method comprises the steps of filling a catalyst for hydrogenating the gases in a vulcanizing tower, heating the temperature of the bed layers of a hydrolysis tower and the vulcanizing tower to 200 ℃ by circulating nitrogen through an electric heating furnace, then mixing metered carbon disulfide, water vapor and limited hydrogen uniformly in a mixing tower, setting three mixing, hydrolyzing and vulcanizing towers in series in a low-temperature vulcanizing period, and vulcanizing the required H 2 S is generated by the reaction of carbon disulfide and water vapor in a hydrolysis tower, and the gas circulation route is as follows: gas circulation compressor, electric heating furnace, mixing tower, hydrolysis reaction tower, vulcanizing tower and heat exchangerGas-water separator-gas recycle compressor; during high temperature sulfiding and strengthening period, the hydrolysis tower and water vapor are removed from the sulfiding system, and the high temperature hydrogenolysis of carbon disulfide provides H for sulfiding 2 S, the whole bed layer is vulcanized fully and completely by temperature and pressure rising, and the gas circulation route is as follows: gas circulation compressor- & gt electric heating furnace- & gt mixing tower- & gt vulcanizing tower- & gt heat exchanger- & gt gas-water separator- & gt gas circulation compressor.
The upper layer of the hydrolysis tower is filled with a protective agent, the lower layer is filled with a hydrolysis catalyst, the filling volume ratio is 1:4-2:3, and gas enters from the upper part and exits from the lower part. The active component of the protective agent is Ti/Al, and the carrier of the hydrolysis catalyst filled in the lower layer is magnesia-alumina spinel.
The limiting hydrogen is hydrogen which is added with 60% -100% of the calculated active component hydrogen sulfide consumption.
The low-temperature vulcanization stage is a vulcanization stage in which the vulcanization temperature is 200-240 ℃ and the sulfur injection amount is 50% of the theoretical sulfur injection amount; the high-temperature vulcanization and the strengthening period are respectively vulcanization stages with the vulcanization temperature of 240-350 ℃ and the sulfur injection amount of 50-75% of the theoretical sulfur injection amount, the vulcanization temperature of 350-420 ℃ and the sulfur injection amount of 75-100% of the theoretical sulfur injection amount.
(3) Stopping the gas circulation compressor in the sulfur discharge period, and introducing H 2 Nitrogen and hydrogen with the content of 2% -5%, and removing H from sulfur-removing tail gas through a purifying tower 2 S is exhausted after the step S, and active components of the desulfurizing agent filled in the purifying tower are Cu/C or Cu/Al 2 O 3 And the gas enters from the lower part and goes out from the upper part, the desulfurizing agent penetrated by the lower part through vulcanization is discharged after desulfurization, a new agent with a corresponding volume is replenished from the upper end, and the discharged desulfurizing agent is used as a gas mercury removing agent.
The gas venting route is as follows: electric heating furnace, mixing tower, vulcanizing tower, purifying tower and emptying. The temperature of the bed layer in the sulfur removal period is 350-420 ℃ and the bed layer is left to be exported H 2 S＜50mg/m 3 And (5) cutting off the power supply to heat the furnace, cooling the bed to 70 ℃, stopping hydrogen distribution, and performing the next operation.
(4) And (5) oxygen-dispensing passivation treatment. The oxygen-preparing passivation treatment temperature is 50-70 ℃, the oxygen content is 2-10%, and the gas emptying route is as follows: mixing tower, vulcanizing tower, purifying tower and emptying.
The invention has the beneficial effects that:
the method and the device fundamentally solve the problem that a catalyst is reduced before vulcanization. Firstly, a hydrolysis tower is arranged, and the sulfur supply mode in the low-temperature vulcanization period is changed. Conventional gas hydrogenation catalyst sulfiding operations, sulfiding the desired H 2 S is all the way through CS 2 Hydrogenolysis provides, low temperature sulfiding must provide substantial amounts of H 2 So as to facilitate the hydrogenolysis reaction and meet the hydrogen consumption requirement of the subsequent sulfuration reaction; h required by the low-temperature vulcanization period of the invention 2 S is formed by CS 2 And steam are generated in a hydrolysis tower to generate H 2 S does not need H 2 Has no concern of hydrogen control, and CS at about 200 DEG C 2 The hydrolysis conversion rate reaches 99 percent, and H cannot be supplied in the earlier stage of vulcanization 2 S problem. Second, H 2 Only meets the hydrogen consumption requirement of the vulcanization reaction, and the theoretical consumption is as low as H 2 Less than half of the S substance, even if 100% of the calculated amount of hydrogen is added, the content is less than 0.5%, and CO is not contained in the sulfur gas, so that the oxidation state active component of the lower catalyst which is similar to the conventional sulfur and is not penetrated by sulfur can not be possibly influenced by H in the coke oven gas 2 And CO reduction. In a word, the invention creatively sets the hydrolysis tower for sulfur supply in the low-temperature sulfuration period, so that the lean hydrogen distribution operation before the catalyst is not vulcanized and penetrated is possible, thereby fundamentally avoiding the problem that the catalyst is reduced before sulfuration.
The process is flexible in operation and low in hydrogen consumption. The process of the invention is in low temperature vulcanization, high temperature vulcanization and strengthening stage, the vulcanized gas is circulated, and the circulation route is respectively: gas circulation compressor, electric heating furnace, mixing tower, hydrolysis reaction tower, vulcanizing tower, heat exchanger, gas-water separator and gas circulation compressor; gas circulation compressor- & gt electric heating furnace- & gt mixing tower- & gt vulcanizing tower- & gt heat exchanger- & gt gas-water separator- & gt gas circulation compressor. In the sulfur removal and passivation stage of the process, the gas operation is single-vent, and the routes are respectively as follows: electric heating furnace- & gt mixing tower- & gt vulcanizing tower- & gt purifying tower- & gt emptying; mixing tower, vulcanizing tower, purifying tower and emptying. According to the requirements of different stages, the actual operation flexibly cuts off the hydrolytic tower and other equipment from the gas operation system or shuts down the gas circulation compressor, the electric heating furnace and other equipment. In addition, the invention is used for pouringIn the low-temperature vulcanization stage, sulfur is 0-50% of theoretical sulfur feeding amount, and only 0.5% of H is needed 2 And the gas circulates in the vulcanization period, H 2 The method can enrich and recycle the sulfur gas system, and the hydrogen consumption in the whole vulcanization process is reduced by more than 90 percent compared with the conventional gas hydrogenation catalyst vulcanization operation.
The dosage of the vulcanizing agent is small, the vulcanizing time is short, and the vulcanizing effect is good. The conventional vulcanization process mainly involves the following reactions:
CS 2 +4H 2 =2H 2 S+CH 4 ΔH 0 =－240KJ /mol
MoO 3 +2H 2 S+H 2 =MoS 2 +3H 2 O ΔH 0 =－48.2KJ /mol
9CoO+8H 2 S+H 2 =Co 9 S 8 +9H 2 O ΔH 0 =－13.4KJ /mol
it can be seen that the strong exotherm of the vulcanization process is mainly due to CS 2 Hydrogenolysis to form H for sulfidation 2 S, so conventional vulcanization often causes local overheating to lead to temperature runaway, and sulfur injection speed has to be slowed down or even stopped, so that the temperature is prevented from rising to sinter the catalyst. And gradually recovering the sulfur injection amount after the temperature of the catalyst bed is controllable. The invention has the required H in the low-temperature vulcanization period 2 S is formed by CS 2 And steam is generated in the hydrolysis tower, so that strong exothermic reaction does not occur in the vulcanizing tower, the temperature rise in the sulfur injection process is stable, sulfur can be injected on duty like wet vulcanization, the sulfur injection efficiency is high, and the vulcanization time is shortened. In general, the main sulfur consumption period of the catalyst in the vulcanization process is the low-temperature vulcanization period which is not penetrated by the catalyst bed layer and reaches the high-temperature vulcanization period and the strengthening period, and only H in the vulcanized gas is needed 2 The concentration of S is high, usually 10 to 40g/m 3 ，H 2 The consumption of S is very small, and the cyclic vulcanization well meets the requirement: sulfur injection is only required to be carried out in a small amount in the high temperature period and the strengthening period, H 2 S is enriched in the sulfuration gas system, and the concentration is higher and higher. Conventional on-site vulcanization usually adopts a single-cycle emptying route, and the vulcanized waste gas is directly emptied and discharged, so that the environment is seriously polluted, the use efficiency of the vulcanizing agent is low, and the vulcanizing agent is especially lowIn the high-temperature vulcanizing period and the strengthening period, almost all vulcanizing agents are emptied and wasted, so that the consumption of the vulcanizing agents is saved by about half compared with that of the conventional gas hydrogenation catalyst. In addition, as described above, the catalyst of the present invention is not reduced before vulcanization, and the temperature rise in the vulcanization process is stable, so that the vulcanization effect is good.
Green and economical. First, the exhaust emission is small in the whole external presulfiding process. In the low-temperature vulcanization, high-temperature vulcanization and strengthening stages, the process of the invention has the advantages that the vulcanized gas is circulated, and compared with the conventional vulcanization, the process has almost no exhaust emission. Second, the waste gas composition is simpler than coke oven gas, and is easy to purify. The chemical reaction of the process in the vulcanization stage is as follows:
CS 2 +2H 2 O= CO 2 +2H 2 S
MoO 3 +2H 2 S+H 2 =MoS 2 +3H 2 O
9CoO+8H 2 S+H 2 =Co 9 S 8 +9H 2 O
3NiO+2H 2 S+H 2 =Ni 3 S 2 +3H 2 O
Fe 2 O 3 +3H 2 S= Fe 2 S 3 +3H 2 O
the main component of the waste gas is nitrogen, hydrogen and CO 2 Simple in composition, and the harmful component is a small quantity of H 2 S, because the gas quantity is small, the desulfurization load is low, and compared with organic sulfur such as thiophene, mercaptan and the like in coke oven gas, the sulfur waste gas is easy to desulfurize; third, cu/C or Cu/Cu/Al 2 O 3 The catalyst is used as a gas mercury removal agent after desulfurization. Aiming at the advantages of small amount of vulcanized waste gas, low desulfurization load and early discharge H 2 S concentration is high, dry desulfurization is adopted, and desulfurizing agent Cu/C or Cu/Al is selected 2 O 3 High sulfur resistance and high desulfurizing precision. And Cu/C or Cu/Al 2 O 3 The catalyst has excellent mercury removal activity after desulfurization, can be used for high-efficiency removal of trace mercury in natural gas, and can produce economic benefit while purifying waste gas produced by the sulfur-free gas hydrogenation catalyst.
The sulfuration-free gas hydrogenation catalyst produced by the method is ready to use without activating treatment before use. As previously mentioned, in-situ vulcanization becomes increasingly difficult to achieve as national environmental requirements become more stringent. The gas device external presulfiding catalyst has little industrial application, and an important reason is that no matter what external presulfiding method is adopted, the prepared external presulfiding catalyst has a concentrated sulfur release and concentrated heat release process during use, the possible bed temperature is difficult to control during startup operation, the problem of sulfur-containing waste gas treatment and emission is also brought, the operation difficulty before the system is involved in production and the problem of emission are not greatly different from the actual on-site vulcanization, and the on-site packaging and the on-site use cannot be realized. The sulfur-free gas hydrogenation catalyst produced by the invention improves the traditional in-device dry method sulfur, fundamentally solves the problem that the catalyst is reduced before sulfur curing, and after sulfur curing, deep sulfur removal and passivation are carried out, thereby avoiding the difficulty that a new agent enters a system due to heat release and sulfur release, and avoiding the problem that the new agent cannot enter a system due to H 2 The too high S is forced to empty and discharge coke oven gas, and the production is not influenced by the urgent discharge of the system due to the overtemperature of the bed layer. The sulfur-free gas hydrogenation catalyst can be used by coke oven gas manufacturers provided with two towers for pre-hydrogenation and auxiliary lines for primary hydrogenation and secondary hydrogenation, and can be used for realizing no coke oven gas emission, no production stop and replacement, no activation treatment and instant assembly.
Drawings
FIG. 1 is a flow chart of a production process of a sulfur-free gas hydrogenation catalyst.
In the figure, 1 is a gas circulation compressor, 2 is an electric heating furnace, 3 is hydrogen, 4 is a mixing tower, 5 is carbon disulfide and water vapor, 6 is a hydrolysis reaction tower, 7 is an impregnating solution, 8 is a carrier, 9 is drying, 10 is roasting, 11 is a vulcanizing tower, 12 is a purifying tower, 13 is a vent, 14 is a heat exchanger, and 15 is a gas-water separator.
Examples
The present invention will now be described in further detail with reference to the drawings and specific embodiments, but the manner in which the same are provided is by way of illustration only and should not be construed to limit the scope of the invention.
Example 1
Production 15m 3 A sulfur-free FeMo pre-hydrogenation catalyst.
Preparation of FeMo/Al 2 O 3 A gas hydrogenation catalyst. Weigh 0.93 ton of Fe (NO) 3 ) 3 ·9H 2 O, 0.97 ton (NH) 4 ) 6 Mo 7 O 24 ·4H 2 O, with 4.92m 3 Dissolving in water, regulating pH value of the soaking solution 7 to 5.5 with phosphoric acid, and selecting spherical Al with strength of 120N/granule and water content of 65% of 9.34 ton 2 O 3 The support 8 is immersed in an equal volume for 1 hour and 40 minutes, dried at 100℃for 3 hours to 9 hours (reference numeral is dry instead of baking, and if no reference numeral is present, baking and drying are not so-called), and baked at 350℃for 4 hours to 10 hours.
And (5) vulcanizing. The catalyst prepared through the steps is filled in a vulcanizing tower 11, and the upper layer of a hydrolysis reaction tower 6 is filled with 3m 3 Ti/Al protective agent, lower layer 12m 3 The hydrolysis catalyst of magnesia-alumina spinel carrier has gas inlet and outlet. Preparation 558LCS 2 160kg of water vapor. The temperature of the bed layers of the hydrolysis tower and the vulcanizing tower is firstly increased to 200 ℃ by circulating nitrogen through an electric heating furnace, and then 50L/h of carbon disulfide, 28.6kg/h of water vapor 5 and 6.64 m are added 3 Hydrogen 3/h (theoretical hydrogen supply 11.07 m) 3 And/h) uniformly mixing in a mixing tower 4, wherein the gas circulation route is as follows: the method comprises the steps of a gas circulation compressor 1, an electric heating furnace 2, a mixing tower 4, a hydrolysis reaction tower 6, a vulcanizing tower 11, a heat exchanger 14, a gas-water separator 15 and a gas circulation compressor 1, wherein the temperature of a catalyst bed is kept at 240 ℃, and the pressure of a circulation system is 0.5-0.7 MPa. After carbon disulfide 279L is injected, water vapor is stopped being added, the hydrolysis tower 6 is cut off from the vulcanization system, and the gas circulation route is as follows: gas circulation compressor 1- & gt electric heating furnace 2- & gt mixing tower 4- & gt vulcanizing tower 11- & gt heat exchanger 14- & gt gas-water separator 15- & gt gas circulation compressor 1- & gt is matched with H with 5% content 2 Raising the temperature of the bed layer of the vulcanizing tower to 350 ℃ at the speed of 35 ℃/h, entering a high-temperature vulcanizing period, adjusting the carbon disulfide to 60L/h until sulfur injection is 418L (75% of theoretical sulfur feeding amount), raising the temperature of the bed layer of the vulcanizing tower to 420 ℃ at the speed of 70 ℃/h, entering a reinforcing period, adjusting the pressure of a circulating system to 0.7-1.2 MPa, and adjusting the carbon disulfideThe total volume is 100L/h, and the sulfur injection is finished (100% of theoretical sulfur feeding amount) by 558L.
(3) And (5) sulfur removal. Stopping the gas circulation compressor, and introducing H 2 Nitrogen and hydrogen with the content of 2 percent, and the tail gas with the sulfur removal is subjected to H removal by the purifying tower 12 2 S is emptied, and the purifying tower is filled with 12m 3 Cu/C desulfurizing agent. The gas venting route is as follows: electric heating furnace 2- & gt mixing tower 4- & gt vulcanizing tower 11- & gt purifying tower 12- & gt emptying 13. The temperature of the bed layer in the sulfur removal period is 350-420 ℃ and the bed layer is left to be exported H 2 S＜50mg/m 3 And (5) cutting off the power supply to heat the furnace, cooling the bed to 70 ℃, stopping hydrogen distribution, and performing the next operation.
(4) And (5) passivating. The oxygen-preparing passivation treatment temperature is 50 ℃, the oxygen content is 10%, and the gas emptying route is as follows: mixing column 4- & gt vulcanizing column 11- & gt purifying column 12- & gt emptying 13.
The catalyst was cooled to room temperature and then discharged for packaging. Removal of 9 from the purification column 9m 3 The desulfurizing agent is used as natural gas mercury removing agent.
Example 2
Production 30 m 3 A sulfur-free CoMo gas hydrogenation catalyst.
Preparation of CoMo/Al 2 O 3 A gas hydrogenation catalyst. Weigh 1.84 tons of Co (NO) 3 ) 2 ·6H 2 O, 2.19 tons (NH) 4 ) 6 Mo 7 O 24 ·4H 2 O, with 11.05m 3 Dissolving in water, regulating pH value of the soaking solution 7 to 6.2 with phosphoric acid, and selecting spherical Al with strength of 142N/granule and water content of 71% of 18.69 ton 2 O 3 The carrier 8 is immersed in the solution for 1 hour and 40 minutes in an equal volume, dried for 2.5 hours to 9 at 110 ℃ and baked for 3.2 hours to 10 at 450 ℃.
And (5) vulcanizing. The catalyst prepared through the steps is filled in a vulcanizing tower 11, and 12m of the upper layer of a hydrolysis reaction tower 6 is filled 3 Ti/Al protective agent, lower layer 18m 3 The hydrolysis catalyst of magnesia-alumina spinel carrier has gas inlet and outlet. Preparation 1000LCS 2 290kg of water vapor. Firstly, the temperature of the bed layers of a hydrolysis tower and a vulcanizing tower is increased to 200 ℃ by circulating nitrogen through an electric heating furnace, and then 50L/h of carbon disulfide, 51.2kg/h of water vapor 5 and 19.83m are added 3 Hydrogen 3/h (theoretical hydrogen supply 19.83m 3 And/h) uniformly mixing in a mixing tower 4, wherein the gas circulation route is as follows: gas and its preparation methodThe method comprises the steps of circulating compressor 1, electric heating furnace 2, mixing tower 4, hydrolysis reaction tower 6, vulcanizing tower 11, heat exchanger 14, gas-water separator 15, gas circulating compressor 1, wherein the temperature of a catalyst bed is kept at 200 ℃, and the pressure of a circulating system is 0.5-0.7 MPa. After 500L of carbon disulfide is injected, water vapor is stopped being added, the hydrolysis tower 6 is cut off from the vulcanization system, and the gas circulation route is as follows: gas circulation compressor 1- & gt electric heating furnace 2- & gt mixing tower 4- & gt vulcanizing tower 11- & gt heat exchanger 14- & gt gas-water separator 15- & gt gas circulation compressor 1- & gt is matched with H with 10% content 2 And (3) raising the temperature of the bed layer of the vulcanizing tower to 240 ℃ at a speed of 35 ℃/h, entering a high-temperature vulcanizing period, adjusting the carbon disulfide to 0L/h until sulfur injection is 500L (50% of theoretical sulfur feeding amount), raising the temperature of the bed layer of the vulcanizing tower to 350 ℃ at a speed of 60 ℃/h, entering a strengthening period at a circulating system pressure of 0.7-1.2 MPa, and adjusting the carbon disulfide to 200L/h until sulfur injection is 750L (75% of theoretical sulfur feeding amount) is finished.
(3) And (5) sulfur removal. Stopping the gas circulation compressor, and introducing H 2 Nitrogen and hydrogen with 5 percent of content and sulfur-removing tail gas is removed H by the purifying tower 12 2 S is emptied, and the purifying tower 12 is filled with 20m 3 Cu/C desulfurizing agent. The gas venting route is as follows: electric heating furnace 2- & gt mixing tower 4- & gt vulcanizing tower 11- & gt purifying tower 12- & gt emptying 13. The temperature of the bed layer in the sulfur removal period is 350-420 ℃ and the bed layer is left to be exported H 2 S＜50mg/m 3 And (5) cutting off the power supply to heat the furnace, cooling the bed to 70 ℃, stopping hydrogen distribution, and performing the next operation.
(4) And (5) passivating. The oxygen-preparing passivation treatment temperature is 70 ℃, the oxygen content is 2%, and the gas emptying route is as follows: mixing column 4- & gt vulcanizing column 11- & gt purifying column 12- & gt emptying 13.
The catalyst was cooled to room temperature and then discharged for packaging. 17 m from the purification column 3 The desulfurizing agent is used as natural gas mercury removing agent.
Example 3
Production 20m 3 A sulfur-free NiMo coke oven gas secondary hydrogenation catalyst.
Preparation of NiMo/Al 2 O 3 A gas hydrogenation catalyst. Weigh 1.63 tons of Ni (NO) 3 ) 2 ·6H 2 O, 1.68 ton (NH) 4 ) 6 Mo 7 O 24 ·4H 2 O, 7.74m 3 Dissolving in water, regulating pH of the soaking solution 7 to 6.8 with phosphoric acid, and selecting spherical Al with strength of 165N/granule and water content of 78% of 12.21 ton 2 O 3 The carrier 8 is immersed in the solution for 1 hour and 40 minutes in an equal volume, dried for 2 hours to 9 at 120 ℃ and baked for 2.5 hours to 10 at 550 ℃.
And (5) vulcanizing. The catalyst prepared through the steps is filled in a vulcanizing tower 11, and the upper layer of a hydrolysis reaction tower 6 is filled with 6m 3 Ti/Al protective agent, lower layer 14m 3 The hydrolysis catalyst of magnesia-alumina spinel carrier has gas inlet and outlet. 800LCS 2 230kg of water vapor. Firstly, the temperature of the bed layers of a hydrolysis tower and a vulcanizing tower is increased to 200 ℃ by circulating nitrogen through an electric heating furnace, and then 50L/h of carbon disulfide, 41.0kg/h of water vapor 5 and 12.69m are added 3 Hydrogen 3/h (theoretical hydrogen supply 15.87 m) 3 And/h) uniformly mixing in a mixing tower 4, wherein the gas circulation route is as follows: the method comprises the steps of a gas circulation compressor 1, an electric heating furnace 2, a mixing tower 4, a hydrolysis reaction tower 6, a vulcanizing tower 11, a heat exchanger 14, a gas-water separator 15 and a gas circulation compressor 1, wherein the temperature of a catalyst bed is kept to be 220 ℃, and the pressure of a circulation system is kept to be 0.5-0.7 MPa. After 400L of carbon disulfide is injected, water vapor is stopped being added, the hydrolysis tower is cut off from the vulcanization system, and the gas circulation route is as follows: gas circulation compressor 1- & gt electric heating furnace 2- & gt mixing tower 4- & gt vulcanizing tower 11- & gt heat exchanger 14- & gt gas-water separator 15- & gt gas circulation compressor 1 is matched with H with the content of 7.5% 2 And (3) raising the temperature of the bed layer of the vulcanizing tower to 295 ℃ at a speed of 40 ℃/h, entering a high-temperature vulcanizing period, adjusting the carbon disulfide to 68L/h until sulfur injection is 500L (62.5% of theoretical sulfur feeding amount), raising the temperature of the bed layer of the vulcanizing tower to 385 ℃ at a speed of 75 ℃/h, enabling the pressure of a circulating system to be 0.7-1.2 MPa, entering a strengthening period, adjusting the carbon disulfide to 150L/h, and ending the sulfur injection to 700L (87.5% of theoretical sulfur feeding amount).
(3) And (5) sulfur removal. Stopping the gas circulation compressor, and introducing H 2 Nitrogen and hydrogen with 3.5 percent of content, and the tail gas of sulfur removal is removed H by the purifying tower 12 2 S is emptied, and the purifying tower is filled with 15m 3 Cu/Al 2 O 3 Desulfurizing agent. The gas venting route is as follows: electric heating furnace 2- & gt mixing tower 4- & gt vulcanizing tower 11- & gt purifying tower 12- & gt emptying 13. The temperature of the bed layer in the sulfur removal period is 350-420 ℃ and the bed layer is left to be exported H 2 S＜50mg/m 3 Power-off heating furnaceAnd cooling the bed to 70 ℃, stopping hydrogen distribution, and performing the next operation.
(4) And (5) passivating. The oxygen-preparing passivation treatment temperature is 60 ℃, the oxygen content is 6%, and the gas emptying route is as follows: mixing column 4- & gt vulcanizing column 11- & gt purifying column 12- & gt emptying 13.
The catalyst was cooled to room temperature and then discharged for packaging. Discharge from the purification column 13m 3 The desulfurizing agent is used as natural gas mercury removing agent.
Claims (9)
1. The production process of the sulfur-free gas hydrogenation catalyst is characterized by comprising the following steps of:
preparation of FeMo/Al by isovolumetric impregnation 2 O 3 、CoMo/Al 2 O 3 、NiMo/Al 2 O 3 A gas hydrogenation catalyst;
the method comprises the steps of filling a catalyst for hydrogenating the gases in a vulcanizing tower, heating the temperature of the bed layers of a hydrolysis tower and the vulcanizing tower to 200 ℃ by circulating nitrogen through an electric heating furnace, then mixing metered carbon disulfide, water vapor and limited hydrogen uniformly in a mixing tower, setting three mixing, hydrolyzing and vulcanizing towers in series in a low-temperature vulcanizing period, and vulcanizing the required H 2 S is generated by the reaction of carbon disulfide and water vapor in a hydrolysis tower, and the gas circulation route is as follows: gas circulation compressor, electric heating furnace, mixing tower, hydrolysis reaction tower, vulcanizing tower, heat exchanger, gas-water separator and gas circulation compressor; during the high-temperature vulcanization and reinforcement period, the hydrolysis tower and the water vapor are cut off from the vulcanization system, and H with the content of 5% -10% is added 2 High temperature hydrogenolysis of carbon disulphide to provide H for sulphurisation 2 S, the whole bed layer is vulcanized fully and completely by temperature and pressure rising, and the gas circulation route is as follows: gas circulation compressor- & gt electric heating furnace- & gt mixing tower- & gt vulcanizing tower- & gt heat exchanger- & gt gas-water separator- & gt gas circulation compressor;
the active component of the protective agent filled in the upper layer of the hydrolysis tower is Ti/Al, and the carrier of the hydrolysis catalyst filled in the lower layer is magnesia-alumina spinel;
(3) Stopping the gas circulation compressor in the sulfur removal period, introducing nitrogen and hydrogen, and removing H from the sulfur removal tail gas through a purifying tower 2 S, emptying after the step S;
(4) And (5) after cooling, carrying out oxygen-matched passivation treatment.
2. The production process of the sulfur-free gas hydrogenation catalyst according to claim 1, wherein the isovolumetric impregnation method is one-step impregnation, and the pH value of the impregnation solution is 5.5-6.8.
3. The production process of the sulfur-free gas hydrogenation catalyst according to claim 1, wherein the hydrolysis tower in the step (II) is filled with a protective agent at the upper layer and a hydrolysis catalyst at the lower layer, the filling volume ratio is 1:4-2:3, and gas is fed in and fed out from the upper layer.
4. The production process of the sulfur-free gas hydrogenation catalyst according to claim 1, wherein the limiting hydrogen in the step (a) is hydrogen which is 60% -100% of the calculated active component hydrogen sulfide consumption.
5. The production process of the sulfur-free gas hydrogenation catalyst according to claim 1, wherein the low-temperature vulcanization period in the step (a vulcanization period is a vulcanization period in which the vulcanization temperature is 200-240 ℃ and the sulfur injection amount is 50% of the theoretical sulfur injection amount.
6. The production process of the sulfur-free gas hydrogenation catalyst according to claim 1, wherein the high-temperature vulcanization period in the step is 240-350 ℃ in vulcanization temperature, and the sulfur injection amount is 50-75% of the theoretical sulfur injection amount; and a vulcanization stage in which the vulcanization temperature in the reinforcement stage is 350-420 ℃ and the sulfur injection amount is 75-100% of the theoretical sulfur injection amount.
7. The process for producing the sulfur-free gas hydrogenation catalyst according to claim 1, wherein the desulfurizing agent active component filled in the purifying tower is Cu/C or Cu/Al 2 O 3 Gas enters downwards and exits upwards, and Cu/C or Cu/Al penetrated by lower vulcanization 2 O 3 Discharging after desulfurization as gas mercury removing agent, and supplementing from upper endVolume of the new agent.
8. The production process of the sulfur-free gas hydrogenation catalyst according to claim 1, wherein the oxygen distribution passivation treatment temperature in the step (4) is 50-70 ℃ and the oxygen content is 2-10%.
9. The process for producing a sulfur-free gaseous hydrogenation catalyst according to claim 1, wherein the catalyst is ready-to-use without an activation treatment prior to use.
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| CN111876205A (en) * | 2020-07-30 | 2020-11-03 | 武汉科林化工集团有限公司 | Gas hydrogenation catalyst vulcanization and vulcanization waste gas treatment and discharge process |
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| GB1032211A (en) * | 1963-10-24 | 1966-06-08 | Exxon Research Engineering Co | Hydrofining process |
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