CN103657740B - Step-by-step sulfuration method of sulfur tolerant shift catalyst - Google Patents
Step-by-step sulfuration method of sulfur tolerant shift catalyst Download PDFInfo
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Abstract
The invention discloses a step-by-step sulfuration method of a sulfur tolerant shift catalyst, belongs to the technical field of pre-sulfuration treatment of a carbon monoxide sulfur tolerant shift catalyst, and particularly relates to a method for rapidly sulfurating a cobalt-molybdenum series sulfur tolerant shift catalyst. Specific to the condition of insufficient sulfuration condition after a new up-conversion device or old device is reconstructed at present, particularly less warming means, a step-by-step sulfuration method is adopted, namely, a method of rapid pre-sulfuration in a medium-low temperature device and online medium-high temperature short-time intense sulfuration is adopted, thus the sulfuration time is shortened, the sulfuration cost is lowered, and the sulfuration effect achieves a sulfuration effect of a conventional catalyst.
Description
Technical field
A kind of step-by-step sulfuration method of sulfur tolerant shift catalyst, belongs to co surfer-resistant shift catalyst presulfurization processing technology field, is specifically related to the method for Co-Mo sulfur-tolerant shift catalyst being carried out to short vulcanization process.
Background technology
Sulfur-resistant transformation catalyst is successfully applied to fertilizer industry, achieves significant economic benefit.Sulfur-resistant transformation catalyst adopts Co-Mo metallic element to be active component mostly, and is dispersed in Al with oxidation state
2o
3, Al
2o
3+ Re
2o
3on porous carriers such as (Re represent rare earth element), it uses wide temperature region, shift activity high, there is not the features such as sulfur poisoning problem, since development always pay close attention to by everybody.The catalyst of new production just must have activity by sulfuration to sulphided state before use, and the quality of sulfidation directly affects shift activity and the stability of catalyst, directly affects its service life to a certain extent.Therefore, the sulfuration of sulfur-resistant transformation catalyst is one of the first step and committed step of its application.
The sulfuration process of sulfur-resistant transformation catalyst successively can be divided into presulfurization and online sulfuration from cure time, and catalyst is first vulcanizated then blanketing with inert gas to driving by presulfurization exactly before driving in fixture or outside device; Online sulfuration is directly driven after referring to carry out sulfuration when driving by the process gas of sulfur-bearing agent.The two respectively has pluses and minuses, but adopts the many of presulfurization due to the current producer of economic cause, can also be divided into circulating sulfuration and disposablely pass through sulfuration during presulfurization according to vulcanization.Circulating sulfuration refers to that sulfiding gas carries out sulfuration through beds after being warmed up to uniform temperature, then suppress to the sulfuration of temperature elevation system continuation above by compressor again through heat exchange cooling, whole gas is closed circulating sulfuration, the place of emptying is uniquely needed to be that circulating sulfuration by a part of gas emptying process and then will supplement a part of sulfiding gas when not meeting cures requirements to gas content, this vulcanization economy, but require special sulfuration pipeline, and after sulfuration, most vulcanizing equipment can not be used as his use due to adsorption of hydrogen sulfide corrosion.Disposable stable by sulfiding gas composition, sulfiding gas is by directly emptying after reactor, but the waste of this vulcanization is serious, consumes comparatively large, in recent years increasing price of raw materials and environmental requirement strict, disposablely substantially to be discarded by sulfuration.Online sulfuration and presulfurization disposable by similar, difference is that process gas sulfuration use in online sulfuration, and presulfurization is then to prepare special sulfiding gas, and sulfuration is vulcanized by moisture online, and presulfurization is dry gas sulfuration.Online sulfuration is due to the generation also along with transformationreation while sulfuration in addition, sulfuration overheating problem ubiquity, and therefore the online most important controlling unit of sulfuration is exactly reply way when preventing overtemperature and overtemperature.
Traditional natural vulcanization method, utilizes a small amount of H contained by wet conversion gas of heat exchanger outlet about 200 DEG C
2s carries out slow sulfuration to catalyst.This vulcanization process not only required time greatly extends, and sulfuration rear catalyst activity does not far reach expection requires (or require higher inlet temperature, or low change outlet of still CO is higher), activity decay is also very fast, thus do not reach due economic benefit, therefore natural vulcanization method is worthless.
" vulcanizing agent of sulfur-resistant CO conversion catalyst and the application thereof " of Chinese patent ZL 89102614.2 discloses a kind of vulcanization process of sulfur-resistant CO conversion catalyst, it is after beds hot(test)-spot temperature reaches 200 DEG C, sulphur or sulfur-bearing ammonium salt or metal sulfide and coal are prepared burden by weight 0.0015 ~ 0.02:1, insert in the simple stationary gas producer of synthesis ammonia plant, control to produce H while furnace temperature 900 DEG C ~ 1100 DEG C makes generation syngas for synthetic ammonia
2s, controls H in unstripped gas
2content 12 ~ the 60g/m of S
3transformation catalyst is processed, until catalyst bed temperature 350 ~ 450 DEG C, imports and exports H
2till S content is constant.This sulfuration belongs to conventional online process gas sulfuration, and cure time is long, costly.
Summary of the invention
The technical problem to be solved in the present invention is: overcome the deficiencies in the prior art, provide a kind of fast to catalyst carry out complete cure and presulfurization needed for the few a kind of step-by-step sulfuration method of sulfur tolerant shift catalyst of intensification means.
The technical solution adopted for the present invention to solve the technical problems is: a kind of step-by-step sulfuration method of sulfur tolerant shift catalyst, is characterized in that, comprise middle low-temperature circulating presulfurization and high temperature online short vulcanization two step, its concrete implementing process step is:
1, heat up to change furnace, after reaction bed temperature reaches 200 ~ 220 DEG C, constant temperature 2 ~ 5h, carries out middle low temperature presulfurization; Before sulfuration starts, in first controller, sulfide stress is at 0.2 ~ 2.0MPa, and circulating air air speed is at 400 ~ 1500h
-1, the H in circulating air
2volume fraction control 1 ~ 25%; Vulcanizing agent adopts a small amount of mode repeatedly slowly to add; And the heating rate being controlled beds by the temperature controlling the addition of vulcanizing agent or circulating air 40 ~ 100 DEG C/h, H
2s concentration is at 20 ~ 40g/m
3; Work as H
2after S penetrates beds, slowly strengthen the sulfuration dosage allocated into, keep H in circulating air
2s content is at 40 ~ 60g/m
3, reaction bed temperature is warming up to 300 ~ 320 DEG C, to temperature no longer continues to raise; Continue to improve H in circulating air
2s content to 60 ~ 70g/m
3, vulcanizing agent addition is to maintain H
2s content is in claimed range; After stopping adding vulcanizing agent, continuous 3 analysis of catalyst beds are worked off one's feeling vent one's spleen middle H
2when S content does not change, can be judged as that low temperature presulfurization terminates;
2, when device goes into operation, vulcanizing agent is dropped in process gas, or vulcanizing agent is directly added in beds by pipeline, adopt inert gas that reaction bed temperature is increased to 200 ~ 220 DEG C, again process gas and inert gas are blended together sulfur-bearing process gas according to the ratio of 0.5 ~ 5.0:1, control H in sulfur-bearing process gas
2s content is at 30 ~ 40g/m
3, sulfide stress is 1.0 ~ 5.0MPa, and sulfur-bearing process gas air speed is 400 ~ 3000h
-1, carry out online sulfuration fast; After sulfuration starts, with the heating rate of 40 ~ 130 DEG C/h, reaction bed temperature being increased to 320 ~ 380 DEG C, directly carrying out in catalyst high temperature vulcanized, when occurring that hydrogen sulfide penetrates, continuing to improve reaction bed temperature to 400 ~ 450 DEG C, H
2s content to 40 ~ 70g/m
3, proceed the online sulfuration of high temperature; When stopping adds vulcanizing agent, continuous 3 analysis of catalyst beds are worked off one's feeling vent one's spleen middle H
2when S content does not change, the online sulfuration of middle high temperature terminates.The follow-up program that goes into operation can be carried out simultaneously.
Preferably, the circulating air air speed described in step 1 remains on 500 ~ 1000h
-1.
Preferably, the heating rate of the beds described in step 1 is at 40 ~ 60 DEG C/h.
Preferably, the sulfide stress described in step 1 is at 0.8 ~ 1.6MPa.
Preferably, the heating rate of the beds described in step 2 is 50 ~ 100 DEG C/h.
Preferably, the sulfur-bearing process gas air speed described in step 2 keeps 500 ~ 2000h
-1.
Preferably, the sulfide stress described in step 2 is 1.5 ~ 3.0MPa.
Preferably, the intensification inert gas described in step 2 is nitrogen or argon gas.
In step 1,2, vulcanizing agent addition is to maintain H
2s content is in claimed range.
Wherein, the vulcanizing agent in described presulfurization agent circulating air is selected from hydrogen sulfide (H
2s), carbon disulfide (CS
2), ethyl mercaptan (EM), n-butyl mercaptan (NBM), sulphur oxygen carbon (COS).
Described circulating air is based on inert gas, and allocate the hydrogen of 1 ~ 25% into, hydrogen purity is not less than 99.9%, and oxygen content can not higher than 0.1%.Easily there is catalyst activity component reduction reaction higher than 25% in hydrogen content, can affect vulcanizing agent hydrogenolysis generate H lower than 1%
2s.During sulfuration, reaction is more single, and heat release is the heat release of vulcanizing agent hydrogenolysis and sulfuration heat release mainly, can by controlling the amount of vulcanizing agent and adding speed and carry out control temperature, and thermal discharge is low, can avoid bed overheating problem.
For current new up conversion device or old plant modification after cure condition inadequate, especially the situation that intensification means are few, the present invention adopts step-by-step sulfuration method, the method of presulfurization fast in low-temperature device in namely adopting+online middle high temperature, short time strengthening sulfuration, shorten cure time, reduce sulfuration expense, cure efficiency reaches conventional catalyst cure efficiency simultaneously.During concrete finger employing in-situ presulfurization, because intensification means are few, when during sulfuration, reaction bed temperature cannot be increased to more than 300 ~ 350 DEG C, quick method for pre-sulphuration in low-temperature device in employing, cryogenic vulcanization condition in strengthening, ensureing that under medium and low temperature condition, sulfuration reaches maximum while, realize quick, high performance vulcanization, and then shorten overall cure time.When device goes into operation, in unstripped gas, add sulphur-containing substance (as sulphur, CS
2deng), improve concentration of hydrogen sulfide in unstripped gas in short-term, and improve system pressure, temperature fast, hot stage degree of depth cure time in shortening, improve catalyst vulcanization effect, reduce sulfuration expense, and then reduce total time needed for intensification and sulfuration, solve at present new up conversion device or old plant modification after cure condition not, the halfway problem of sulfuration that especially intensification means are brought less.Adopt substep sulfuration, emptying amount reduces, and sulfuration is easy, safety, pollutes few, has significant economic and social benefit.
Compared with prior art, the beneficial effect that a kind of step-by-step sulfuration method of sulfur tolerant shift catalyst of the present invention has is: adopt step-by-step sulfuration method of the present invention, the quick presulfurization of low-temperature reinforcement namely, the method for the quick online sulfuration of collocation under-stream period high temperature.Strengthen each stage conditions of vulcanization, at guarantee catalyst vulcanization simultaneously completely, realize quick, high performance vulcanization, greatly save sulfuration and intensification required time, reduce sulfuration expense.Solve new equipment or reorganization and expansion device transformation catalyst conditions of vulcanization deficiency, the problem of intensification and sulfuration difficulty.Adopt substep sulfuration, maximum using has conditions of vulcanization, and emptying amount is few, and sulfuration is easy, safety, pollutes few, has significant economic and social benefit.
Detailed description of the invention
be described further a kind of step-by-step sulfuration method of sulfur tolerant shift catalyst of the present invention below in conjunction with specific embodiment, wherein embodiment 1 is most preferred embodiment.
Embodiment 1
50000 m
3/ h hydrogen capacity coal gasification apparatus A, transformation system Co-Mo sulfur-tolerant shift catalyst loading amount 128m
3.After changing sulfur-resistant transformation catalyst in 2011, due to the heating furnace fault that goes into operation, carry out sulfuration according to the inventive method.Beds heats up, and after temperature reaches 215 DEG C, constant temperature 3h, carries out middle low temperature presulfurization; Before sulfuration starts, in first controller, sulfide stress is at 1.0MPa, and circulating air air speed is at 600h
-1, hydrogen is added to (volume ratio: hydrogen: nitrogen=1:9) in nitrogen and enters with nitrogen the stove that goes into operation together and heat; Adopt CS
2carry out sulfuration as curing medium, vulcanizing agent adopts a small amount of mode repeatedly slowly to add; And by control heating rate that the addition of vulcanizing agent or circulating air temperature control beds 50 ~ 60 DEG C/h, H
2s concentration is at 30 ~ 35g/m
3; Work as H
2after S penetrates beds, slowly strengthen the sulfuration dosage allocated into, keep H in recyclegas
2s content is at 38 ~ 40g/m
3, no longer raise when reaction bed temperature being progressively warming up to 300 DEG C; Continue to improve H in circulating air
2s content to 63 ~ 66g/m
3, vulcanizing agent addition is to maintain H
2s content is in claimed range; After stopping adding vulcanizing agent, continuous 3 analysis of catalyst beds are worked off one's feeling vent one's spleen middle H
2when S content does not change, the middle cryogenic vulcanization stage terminates, and cure time is 82h.
When device goes into operation, arrange online sulfuration, adopt CS
2for vulcanizing agent, adopt inert gas that reaction bed temperature is increased to 215 DEG C, then process gas and inert gas are blended together sulfur-bearing process gas according to the ratio of 2.5:1, control H in sulfur-bearing process gas
2s content is at 30 ~ 40g/m
3, sulfide stress is 1.5MPa, and sulfur-bearing process gas air speed is 1500h
-1, carry out online sulfuration fast; After sulfuration starts, fast bed temperature being increased to 350 DEG C with measuring with 70 ~ 100 DEG C/h by the ratio of Controlling Technology gas and inert gas, controlling concentration of hydrogen sulfide in sulfur-bearing process gas and maintaining 40 ~ 50g/m
3between; When occurring that hydrogen sulfide penetrates, continue pressure-raising to 2.5 MPa, lift temperature to 420 ~ 450 DEG C with 70 ~ 100 DEG C/h heating rate, concentration of hydrogen sulfide maintains 50 ~ 60g/m
3between; When vulcanizing agent is added in stopping, when continuous 3 analysis outlet hydrogen sulfide contents are substantially constant, online high temperature vulcanized end.Online cure time is 31h.After air guide success, the total interconversion rate of transformation system CO reaches 98.5%.The sulfuration used time amounts to 113h.
Embodiment 2
450ktNH
3the device B of/a, transformation system Co-Mo sulfur-tolerant shift catalyst loading amount amounts to 158m
3.After changing sulfur-resistant transformation catalyst at the beginning of 2012, high steam shortage, cannot heat exchange temperature raising time, carry out sulfuration according to the inventive method.During middle low temperature presulfurization, beds heats up, and after temperature reaches 200 DEG C, constant temperature 5h, carries out middle low temperature presulfurization; Before sulfuration starts, in first controller, sulfide stress is at 2.0MPa, and circulating air air speed is at 400h
-1, hydrogen is added to (volume ratio: hydrogen: nitrogen=1:4) in nitrogen and enters with nitrogen the stove that goes into operation together and heat; Adopt CS
2carry out sulfuration as curing medium, vulcanizing agent adopts a small amount of mode repeatedly slowly to add; And by control heating rate that the addition of vulcanizing agent or circulating air temperature control beds 40 ~ 50 DEG C/h, H
2s concentration is at 35 ~ 40g/m
3; Work as H
2after S penetrates beds, slowly strengthen the sulfuration dosage allocated into, keep H in recyclegas
2s content is at 56 ~ 60g/m
3, no longer raise when reaction bed temperature being progressively warming up to 320 DEG C; Continue to improve H in circulating air
2s content to 66 ~ 70g/m
3, vulcanizing agent addition is to maintain H
2s content is in claimed range; After stopping adding vulcanizing agent, continuous 3 analysis of catalyst beds are worked off one's feeling vent one's spleen middle H
2when S content does not change, the middle cryogenic vulcanization stage terminates, and cure time is 88h.
When device goes into operation, arrange online sulfuration, adopt CS
2for vulcanizing agent, adopt inert gas that reaction bed temperature is increased to 200 DEG C, then process gas and inert gas are blended together sulfur-bearing process gas according to the ratio of 5.0:1, control H in sulfur-bearing process gas
2s content is at 38 ~ 40g/m
3, sulfide stress is 5.0MPa, and sulfur-bearing process gas air speed is 400h
-1, carry out online sulfuration fast; After sulfuration starts, fast bed temperature being increased to 380 DEG C with measuring with the heating rate of 126 ~ 130 DEG C/h by the ratio of Controlling Technology gas and inert gas, controlling concentration of hydrogen sulfide in sulfur-bearing process gas and maintaining 65 ~ 70g/m
3between; When occurring that hydrogen sulfide penetrates, continue pressurize at 5.0MPa, lift temperature to 445 ~ 450 DEG C with 95 ~ 100 DEG C/h heating rate, concentration of hydrogen sulfide maintains 65 ~ 70g/m
3between; When vulcanizing agent is added in stopping, when continuous 3 analysis outlet hydrogen sulfide contents are substantially constant, online high temperature vulcanized end.Cure time is 54h, and the sulfuration used time amounts to 142h.After air guide success, the total interconversion rate of transformation system CO reaches 98.2%.
Embodiment 3
300ktNH
3the device C of/a, transformation system Co-Mo sulfur-tolerant shift catalyst loading amount amounts to 88m
3.After within 2011, changing sulfur-resistant transformation catalyst, due to electric heater fault, heating power reduces, and carries out sulfuration according to the inventive method.During middle cryogenic vulcanization, beds heats up, and after temperature reaches 220 DEG C, constant temperature 2h, carries out middle low temperature presulfurization; Before sulfuration starts, in first controller, sulfide stress is at 2.0MPa, and circulating air air speed is at 1500h
-1, hydrogen is added to (volume ratio: hydrogen: nitrogen=1:99) in nitrogen and enters with nitrogen the stove that goes into operation together and heat; Adopt CS
2carry out sulfuration as curing medium, vulcanizing agent adopts a small amount of mode repeatedly slowly to add; And by control heating rate that the addition of vulcanizing agent or circulating air temperature control beds 95 ~ 100 DEG C/h, H
2s concentration is at 20 ~ 25g/m
3; Work as H
2after S penetrates beds, slowly strengthen the sulfuration dosage allocated into, keep H in recyclegas
2s content is at 40 ~ 43g/m
3, no longer raise when reaction bed temperature being progressively warming up to 300 DEG C; Continue to improve H in circulating air
2s content to 60 ~ 63g/m
3, vulcanizing agent addition is to maintain H
2s content is in claimed range; After stopping adding vulcanizing agent, continuous 3 analysis of catalyst beds are worked off one's feeling vent one's spleen middle H
2when S content does not change, the middle cryogenic vulcanization stage terminates, and cure time is 40h.
When device goes into operation, arrange online sulfuration, adopt CS
2for vulcanizing agent directly adds in beds, adopt inert gas that reaction bed temperature is increased to 220 DEG C, then process gas and inert gas are blended together sulfur-bearing process gas according to the ratio of 0.5:1, control H in sulfur-bearing process gas
2s content is at 30 ~ 33g/m
3, sulfide stress is 1.0MPa, and sulfur-bearing process gas air speed is 3000h
-1, carry out online sulfuration fast; After sulfuration starts, fast bed temperature being increased to 320 DEG C with measuring with 40 ~ 43 DEG C/h by the ratio of Controlling Technology gas and inert gas, controlling concentration of hydrogen sulfide in sulfur-bearing process gas and maintaining 40 ~ 50g/m
3between; When occurring that hydrogen sulfide penetrates, continue pressure-raising to 2.5 MPa, lift temperature to 400 ~ 405 DEG C with 70 ~ 75 DEG C/h heating rate, concentration of hydrogen sulfide maintains 40 ~ 45g/m
3between; When vulcanizing agent is added in stopping, when continuous 3 analysis outlet hydrogen sulfide contents are substantially constant, online high temperature vulcanized end.Cure time is 27h, and the sulfuration used time amounts to 67h.After air guide success, the total interconversion rate of transformation system CO reaches 98.4%.
Embodiment 4
480ktNH
3the device of/a, transformation system Co-Mo sulfur-tolerant shift catalyst loading amount amounts to 188m
3.After changing sulfur-resistant transformation catalyst at the beginning of 2012, electric heater fault, cannot heat exchange temperature raising time, carry out sulfuration according to the inventive method.During middle low temperature presulfurization, beds heats up, and after temperature reaches 212 DEG C, constant temperature 2.5h, carries out middle low temperature presulfurization; Before sulfuration starts, in first controller, sulfide stress is at 1.5MPa, and circulating air air speed is at 820h
-1, hydrogen is added to (volume ratio: hydrogen: nitrogen=1:19) in nitrogen and enters with nitrogen the stove that goes into operation together and heat; Adopt CS
2carry out sulfuration as curing medium, vulcanizing agent adopts a small amount of mode repeatedly slowly to add; And by control heating rate that the addition of vulcanizing agent or circulating air temperature control beds 60 ~ 65 DEG C/h, H
2s concentration is at 32 ~ 36g/m
3; Work as H
2after S penetrates beds, slowly strengthen the sulfuration dosage allocated into, keep H in recyclegas
2s content is at 48 ~ 51g/m
3, no longer raise when reaction bed temperature being progressively warming up to 315 DEG C; Continue to improve H in circulating air
2s content to 64 ~ 61g/m
3, vulcanizing agent addition is to maintain H
2s content is in claimed range; After stopping adding vulcanizing agent, continuous 3 analysis of catalyst beds are worked off one's feeling vent one's spleen middle H
2when S content does not change, the middle cryogenic vulcanization stage terminates, and cure time is 94h.
When device goes into operation, arrange online sulfuration, adopt CS
2for vulcanizing agent drops in process gas, adopt inert gas that reaction bed temperature is increased to 208 DEG C, then process gas and inert gas are blended together sulfur-bearing process gas according to the ratio of 3.0:1, control H in sulfur-bearing process gas
2s content is at 30 ~ 40g/m
3, sulfide stress is 2.5MPa, and sulfur-bearing process gas air speed is 1800h
-1, carry out online sulfuration fast; After sulfuration starts, fast bed temperature being increased to 350 DEG C with measuring with 80 ~ 85 DEG C/h by the ratio of Controlling Technology gas and inert gas, controlling concentration of hydrogen sulfide in sulfur-bearing process gas and maintaining 40 ~ 50g/m
3between; When occurring that hydrogen sulfide penetrates, continue pressure-raising to 3.0MPa, lift temperature to 440 ~ 450 DEG C with 80 ~ 85 DEG C/h heating rate, concentration of hydrogen sulfide maintains 58 ~ 60g/m
3between; When vulcanizing agent is added in stopping, when continuous 3 analysis outlet hydrogen sulfide contents are substantially constant, online high temperature vulcanized end.Cure time is 63h, and the sulfuration used time amounts to 157h.After air guide success, the total interconversion rate of transformation system CO reaches 98.1%.
Embodiment 5
350ktNH
3the device of/a, transformation system Co-Mo sulfur-tolerant shift catalyst loading amount amounts to 120m
3.After changing sulfur-resistant transformation catalyst at the beginning of 2012, high steam shortage, cannot heat exchange temperature raising time, carry out sulfuration according to the inventive method.During middle low temperature presulfurization, beds heats up, and after temperature reaches 208 DEG C, constant temperature 4h, carries out middle low temperature presulfurization; Before sulfuration starts, in first controller, sulfide stress is at 1.6MPa, and circulating air air speed is at 1000h
-1, hydrogen is added to (volume ratio: hydrogen: nitrogen=1:6) in nitrogen and enters with nitrogen the stove that goes into operation together and heat; Adopt CS
2carry out sulfuration as curing medium, vulcanizing agent adopts a small amount of mode repeatedly slowly to add; And by control heating rate that the addition of vulcanizing agent or circulating air temperature control beds 45 ~ 18 DEG C/h, H
2s concentration is at 28 ~ 31g/m
3; Work as H
2after S penetrates beds, slowly strengthen the sulfuration dosage allocated into, keep H in recyclegas
2s content is at 35 ~ 38g/m
3, no longer raise when reaction bed temperature being progressively warming up to 309 DEG C; Continue to improve H in circulating air
2s content to 65 ~ 68g/m
3, vulcanizing agent addition is to maintain H
2s content is in claimed range; After stopping adding vulcanizing agent, continuous 3 analysis of catalyst beds are worked off one's feeling vent one's spleen middle H
2when S content does not change, the middle cryogenic vulcanization stage terminates, and cure time is 78h.
When device goes into operation, arrange online sulfuration, adopt CS
2for vulcanizing agent drops in process gas, adopt inert gas that reaction bed temperature is increased to 213 DEG C, then process gas and inert gas are blended together sulfur-bearing process gas according to the ratio of 2.0:1, H in Controlling Technology gas
2s content is at 33 ~ 36g/m
3, sulfide stress is 3.5MPa, and sulfur-bearing process gas air speed is 1800h
-1, carry out online sulfuration fast; After sulfuration starts, fast bed temperature being increased to 360 DEG C with measuring with 78 ~ 85 DEG C/h by the ratio of Controlling Technology gas and inert gas, controlling concentration of hydrogen sulfide in sulfur-bearing process gas and maintaining 47 ~ 50g/m
3between; When occurring that hydrogen sulfide penetrates, keep pressure at 3.5 MPa, lift temperature to 420 ~ 425 DEG C with 78 ~ 85 DEG C/h heating rate, concentration of hydrogen sulfide maintains 65 ~ 70g/m
3between; When vulcanizing agent is added in stopping, when continuous 3 analysis outlet hydrogen sulfide contents are substantially constant, online high temperature vulcanized end.Cure time is 29h, and the sulfuration used time amounts to 107h.After air guide success, the total interconversion rate of transformation system CO reaches 98.2%.
Comparative example 1
Device A described in embodiment 1 is when new equipment in 2008 goes into operation presulfurization, the Co-Mo sulfur-tolerant shift catalyst of the identical amount of same model is adopted with embodiment 1, adopt conventional vulcanized mode, process is as follows: when transformation system reaction bed temperature reaches 210 DEG C, hydrogen is added to (volume ratio: hydrogen: nitrogen=1:4) in nitrogen enter with nitrogen the stove that goes into operation together and heat, controlling reactor inlet temperature is 200 ~ 220 DEG C, and pressure about 0.5MPa, gas circulation air speed is about 280h
-1, adopt CS
2carry out sulfuration as curing medium, initial stage entrance concentration of hydrogen sulfide is 5g/m
3, bed temperature rises to 260 ~ 300 DEG C, and hydrogen content maintains about 20%, slowly increases and decreases CS according to beds temperature rise situation and concentration of hydrogen sulfide
2and the addition of hydrogen, after 30h, system outlet occurs that hydrogen sulfide penetrates.Slowly CS is increased and decreased according to beds temperature rise situation and concentration of hydrogen sulfide
2and the addition of hydrogen, treat that stopping adds CS
2, and continuous 3 times analyze outlet hydrogen sulfide contents substantially constant time continue improve bed temperature to 300 ~ 350 DEG C, maintain pressure and gas air speed constant, concentration of hydrogen sulfide is 5 ~ 10g/m
3.When stopping adds CS
2, and when continuous 3 analysis outlet hydrogen sulfide contents are substantially constant, successively bed temperature are progressively increased to 400 ~ 420 DEG C according to method above, then suitably improve pressure to about 0.8Mpa, stop adding CS
2, continuous 3 analysis outlet hydrogen sulfide contents are substantially constant, are 10g/m
3left and right, sulfuration terminates.The sulfuration used time amounts to 144h, and after air guide success, the total interconversion rate of transformation system CO reaches 98.2%.
Comparative example 2
Device B described in embodiment 2 adopted the Co-Mo sulfur-tolerant shift catalyst of the identical amount of same model in 2007 with embodiment 2, and adopt conventional presulfurization mode to carry out catalyst vulcanization, sulfuration atmospheric pressure is 0.5MPa, air speed 240h-1, and hydrogen sulfide content is 5 ~ 10g/m
3, programming rate controls at 30 ~ 40 DEG C/h, and sulfidation is with comparative example 1, and cure time is about 178h, and after air guide success, the total interconversion rate of transformation system CO reaches 98.1%.
Comparative example 3
Device C described in embodiment 3 goes into operation at device in 2007, adopts the Co-Mo sulfur-tolerant shift catalyst of the identical amount of same model with embodiment 2, and adopt conventional presulfurization mode to carry out catalyst vulcanization, sulfuration atmospheric pressure is 0.8MPa, air speed 300 h
-1, hydrogen sulfide content is 8 ~ 12g/m
3, programming rate controls at 30 ~ 40 DEG C/h, and sulfidation is with comparative example 1, and cure time is about 85h, and after air guide success, the total interconversion rate of transformation system CO reaches 98.0%.
The above is only preferred embodiment of the present invention, and be not restriction the present invention being made to other form, any those skilled in the art may utilize the technology contents of above-mentioned announcement to be changed or be modified as the Equivalent embodiments of equivalent variations.But everyly do not depart from technical solution of the present invention content, any simple modification, equivalent variations and the remodeling done above embodiment according to technical spirit of the present invention, still belong to the protection domain of technical solution of the present invention.
Claims (8)
1. a step-by-step sulfuration method of sulfur tolerant shift catalyst, is characterized in that, comprise middle low-temperature circulating presulfurization and high temperature online short vulcanization two step, concrete implementing process step is:
1.1, heat up to change furnace, after reaction bed temperature reaches 200 ~ 220 DEG C, constant temperature 2 ~ 5h, carries out middle low temperature presulfurization; Before sulfuration starts, in first controller, sulfide stress is at 0.2 ~ 2.0MPa, and circulating air air speed is at 400 ~ 1500h
-1, the H in circulating air
2volume fraction control 1 ~ 25%; Vulcanizing agent adopts a small amount of mode repeatedly slowly to add; And the heating rate being controlled beds by the temperature controlling the addition of vulcanizing agent or circulating air 40 ~ 100 DEG C/h, H
2s concentration is at 20 ~ 40g/m
3; Work as H
2after S penetrates beds, slowly strengthen the sulfuration dosage allocated into, keep H in circulating air
2s content is at 40 ~ 60g/m
3, reaction bed temperature is warming up to 300 ~ 320 DEG C, to temperature no longer continues to raise; Continue to improve H in circulating air
2s content to 60 ~ 70g/m
3, vulcanizing agent addition is to maintain H
2s content is in claimed range; After stopping adding vulcanizing agent, continuous 3 analysis of catalyst beds are worked off one's feeling vent one's spleen middle H
2when S content does not change, can be judged as that low temperature presulfurization terminates;
1.2, when device goes into operation, vulcanizing agent is dropped in process gas, or vulcanizing agent is directly added in beds by pipeline, adopt inert gas that reaction bed temperature is increased to 200 ~ 220 DEG C, again process gas and inert gas are blended together sulfur-bearing process gas according to the ratio of 0.5 ~ 5.0:1, control H in sulfur-bearing process gas
2s content is at 30 ~ 40g/m
3, sulfide stress is 1.0 ~ 5.0MPa, and sulfur-bearing process gas air speed is 400 ~ 3000h
-1, carry out online sulfuration fast; After sulfuration starts, with the heating rate of 40 ~ 130 DEG C/h, reaction bed temperature being increased to 320 ~ 380 DEG C, directly carrying out in catalyst high temperature vulcanized, when occurring that hydrogen sulfide penetrates, continuing to improve reaction bed temperature to 400 ~ 450 DEG C, H
2s content to 40 ~ 70g/m
3, proceed the online sulfuration of high temperature; When stopping adds vulcanizing agent, continuous 3 analysis of catalyst beds are worked off one's feeling vent one's spleen middle H
2when S content does not change, the online sulfuration of middle high temperature terminates.
2. a kind of step-by-step sulfuration method of sulfur tolerant shift catalyst according to claim 1, is characterized in that: the air speed of circulating air described in step 1.1 remains on 500 ~ 1000h
-1.
3. a kind of step-by-step sulfuration method of sulfur tolerant shift catalyst according to claim 1, is characterized in that: the heating rate of beds described in step 1.1 is at 40 ~ 60 DEG C/h.
4. a kind of step-by-step sulfuration method of sulfur tolerant shift catalyst according to claim 1, is characterized in that: the heating rate of beds described in step 1.2 is 50 ~ 100 DEG C/h.
5. a kind of step-by-step sulfuration method of sulfur tolerant shift catalyst according to claim 1, is characterized in that: described in step 1.1, sulfide stress is at 0.8 ~ 1.6MPa.
6. a kind of step-by-step sulfuration method of sulfur tolerant shift catalyst according to claim 1, is characterized in that: sulfide stress described in step 1.2 is 1.5 ~ 3.0 MPa.
7. a kind of step-by-step sulfuration method of sulfur tolerant shift catalyst according to claim 1, is characterized in that: the process gas of sulfur-bearing described in step 1.2 air speed keeps 500 ~ 2000h
-1.
8. a kind of step-by-step sulfuration method of sulfur tolerant shift catalyst according to claim 1, is characterized in that: the inert gas of intensification described in step 1.2 is nitrogen or argon gas.
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| US6559092B1 (en) * | 1999-08-17 | 2003-05-06 | Europeenne De Retraitement De Catalyseurs Eurecat | Precarbonisation of a hydrotreatment catalyst |
| CN101733171A (en) * | 2009-12-08 | 2010-06-16 | 华烁科技股份有限公司 | Emptying-free complete circulation vulcanizing method for Co-Mo sulfur tolerant shift catalyst vulcanizing process gas |
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| US6559092B1 (en) * | 1999-08-17 | 2003-05-06 | Europeenne De Retraitement De Catalyseurs Eurecat | Precarbonisation of a hydrotreatment catalyst |
| CN101733171A (en) * | 2009-12-08 | 2010-06-16 | 华烁科技股份有限公司 | Emptying-free complete circulation vulcanizing method for Co-Mo sulfur tolerant shift catalyst vulcanizing process gas |
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