CN103657740A - 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 sulfur-resistant transformation catalyst substep vulcanization process, belongs to co surfer-resistant shift catalyst presulfurization processing technology field, is specifically related to Co-Mo sulfur-tolerant shift catalyst to carry out the method for short vulcanization processing.
Background technology
Sulfur-resistant transformation catalyst is successfully applied to fertilizer industry, has obtained significant economic benefit.It is active component that sulfur-resistant transformation catalyst adopts Co-Mo metallic element 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, does not have the features such as sulfur poisoning problem, since development, has been paid close attention to by everybody always.The catalyst of new production must just have activity by vulcanizing to sulphided state before use, and the quality of sulfidation directly affects shift activity and the stability of catalyst, directly affects to a certain extent its service life.Therefore, the sulfuration of sulfur-resistant transformation catalyst is one of the first step of its application and committed step.
The sulfuration process of sulfur-resistant transformation catalyst successively can be divided into presulfurization and online sulfuration from cure time, presulfurization be exactly before driving first by catalyst in fixture or device vulcanizate then blanketing with inert gas outward to driving; Online sulfuration is directly driven after referring to vulcanize by the process gas of sulfur-bearing agent when driving.The two respectively has pluses and minuses, but because the current producer of economic cause adopts the many of presulfurization, during presulfurization, according to vulcanization, can also be divided into circulating sulfuration and disposable by sulfuration.Circulating sulfuration refers to after sulfiding gas is warmed up to uniform temperature and vulcanizes through beds, then through heat exchange is cooling, by compressor, suppressed to the sulfuration of temperature elevation system continuation above again, whole gas is closed circulating sulfuration, to be circulating sulfuration will not process a part of gas emptying and then supplement a part of sulfiding gas when gas content meets sulfuration and requires in unique place that needs emptying, this vulcanization economy, but require to have special sulfuration pipeline, and after sulfuration, most vulcanizing equipment can not be used as him due to adsorption of hydrogen sulfide corrosion.Disposablely sulfiding gas, consist of stablely, sulfiding gas is by directly emptying after reactor, but the waste of this vulcanization is serious, consumes greatlyr, and increasing price of raw materials and environmental requirement is in recent years strict, disposablely by vulcanizing, substantially discards.Online sulfuration and presulfurization are disposable to be passed through almost, and difference is that online sulfuration is to vulcanize by process gas, and presulfurization is to prepare special sulfiding gas, and sulfuration is moisture sulfuration online, and presulfurization is dry gas sulfuration.When online sulfuration is due to sulfuration in addition, be also accompanied by the generation of transformationreation, sulfuration overheating problem ubiquity, therefore the most important controlling unit of online sulfuration is exactly the reply way while preventing overtemperature and overtemperature.
Traditional natural vulcanization method, utilizes the contained a small amount of H of wet conversion gas of 200 ℃ of left and right of heat exchanger outlet
2s slowly vulcanizes catalyst.This vulcanization process not only required time greatly extends, and sulfuration rear catalyst activity does not far reach expection and requires (or the inlet temperature of having relatively high expectations, or low change outlet of still CO is higher), and activity decay is also very fast, thereby do not reach due economic benefit, so natural vulcanization method is worthless.
The vulcanizing agent of the < < sulfur-resistant CO conversion catalyst of Chinese patent ZL 89102614.2 and application > > thereof disclose a kind of vulcanization process of sulfur-resistant CO conversion catalyst, it is to reach after 200 ℃ when beds hot(test)-spot temperature, by sulphur or sulfur-bearing ammonium salt or metal sulfide and coal by weight 0.0015 ~ 0.02:1 batching, insert in the simple stationary gas producer of synthesis ammonia plant, control and when 900 ℃ ~ 1100 ℃ of furnace temperature make to produce syngas for synthetic ammonia, to produce H
2s, controls H in unstripped gas
2content 12 ~ 60g/m of S
3transformation catalyst is processed, until 350 ~ 450 ℃ of catalyst bed temperatures are imported and exported H
2till S content is constant.This sulfuration belongs to conventional online process gas sulfuration, and cure time is long, and expense is high.
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 and fast catalyst is carried out to a kind of sulfur-resistant transformation catalyst substep vulcanization process complete cure and that the required intensification means of presulfurization are few.
The technical solution adopted for the present invention to solve the technical problems is: a kind of sulfur-resistant transformation catalyst substep vulcanization process, it is characterized in that, and comprise online short vulcanization two steps of middle low-temperature circulating presulfurization and high temperature, its concrete implementing process step is:
1, change furnace is heated up, when reaction bed temperature reaches after 200 ~ 220 ℃, 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 be controlled at 1 ~ 25%; Vulcanizing agent adopts a small amount of mode repeatedly slowly to add; And the heating rate of controlling beds by the control addition of vulcanizing agent or the temperature of circulating air is at 40 ~ 100 ℃/h, H
2s concentration is at 20 ~ 40g/m
3; Work as H
2s penetrates after beds, slowly strengthens the sulfuration dosage of allocating into, keeps H in circulating air
2s content is at 40 ~ 60g/m
3, reaction bed temperature is warming up to 300 ~ 320 ℃, till no longer continuing to raise to temperature; 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; When stopping adding after vulcanizing agent, continuous 3 analysis of catalyst beds middle H that works off one's feeling vent one's spleen
2when S content does not change, can be judged as low temperature presulfurization and finish;
2, when start up, 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 ℃, again process gas and inert gas are blended together to 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, 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 ℃/h, reaction bed temperature is increased to 320 ~ 380 ℃, directly carries out in catalyst high temperature vulcanizedly, when occurring that hydrogen sulfide penetrates, continue to improve reaction bed temperature to 400 ~ 450 ℃, H
2s content to 40 ~ 70g/m
3, proceed high temperature and vulcanize online; When stopping adding vulcanizing agent, continuous 3 analysis of catalyst beds middle H that works off one's feeling vent one's spleen
2when S content does not change, middle high temperature vulcanizes end online.Can carry out the follow-up program that goes into operation 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 ℃/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 ℃/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 of using 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 be take inert gas as main, allocates 1 ~ 25% hydrogen into, and hydrogen purity is not less than 99.9%, and oxygen content can not be 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 mainly the heat release of vulcanizing agent hydrogenolysis and sulfuration heat release, can be by controlling the amount of vulcanizing agent and adding speed to control temperature, and thermal discharge is low, can avoid bed overheating problem.
Inadequate at present new up conversion device or old plant modification after cure condition, especially the situation that intensification means are few, the present invention adopts substep vulcanization process, the method of presulfurization fast in low-temperature device in adopting+online middle high temperature, short time strengthening sulfuration, shorten cure time, reduce sulfuration expense, cure efficiency reaches conventional catalyst cure efficiency simultaneously.While specifically referring to adopt the interior presulfurization of device, because intensification means are few, during sulfuration, reaction bed temperature cannot be increased to 300 ~ 350 ℃ when above, quick method for pre-sulphuration in low-temperature device in employing, cryogenic vulcanization condition in strengthening, guaranteeing that under medium and low temperature condition, sulfuration reaches the maximum while, realizing fast, efficiently vulcanize, and then shorten the total cure time.When start up, in unstripped gas, add sulphur-containing substance (as sulphur, CS
2deng), improve in short-term concentration of hydrogen sulfide in unstripped gas, and improve fast system pressure, temperature, hot stage degree of depth cure time in shortening, improve catalyst vulcanization effect, reduce sulfuration expense, and then reduce intensification and vulcanize required total time, at present new up conversion device or old plant modification after cure condition have been solved inadequate, the halfway problem of sulfuration that especially intensification means are brought less.Adopt substep sulfuration, emptying amount reduces, and vulcanizes easy, safety, and pollution is few, has significant economic and social benefit.
Compared with prior art, the beneficial effect that a kind of sulfur-resistant transformation catalyst substep vulcanization process of the present invention has is: adopt substep vulcanization process of the present invention, i.e. and the middle quick presulfurization of low-temperature reinforcement, collocation under-stream period high temperature is the method for online sulfuration fast.Strengthen each stage conditions of vulcanization,, realize fast at assurance catalyst vulcanization simultaneously completely, efficiently vulcanize, greatly save and vulcanize and intensification required time, reduce sulfuration expense.Solved new equipment or reorganization and expansion device transformation catalyst conditions of vulcanization not enough, heated up and vulcanize difficult problem.Adopt substep sulfuration, maximum using has conditions of vulcanization, and emptying amount is few, vulcanizes easy, safety, pollutes less, has significant economic and social benefit.
The specific embodiment
below in conjunction with specific embodiment, a kind of sulfur-resistant transformation catalyst substep of the present invention vulcanization process is described further, 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.In 2011, change after sulfur-resistant transformation catalyst, due to the heating furnace fault that goes into operation, according to the inventive method, vulcanize.Beds heats up, and temperature reaches after 215 ℃, and 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) enter together with nitrogen the stove that goes into operation and heat in nitrogen; Adopt CS
2as curing medium, vulcanize, vulcanizing agent adopts a small amount of mode repeatedly slowly to add; And by controlling the addition of vulcanizing agent or the heating rate of circulating air temperature control beds at 50 ~ 60 ℃/h, H
2s concentration is at 30 ~ 35g/m
3; Work as H
2s penetrates after beds, slowly strengthens the sulfuration dosage of allocating into, keeps H in recyclegas
2s content is at 38 ~ 40g/m
3, when reaction bed temperature is progressively warming up to 300 ℃, no longer raise; 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; When stopping adding after vulcanizing agent, continuous 3 analysis of catalyst beds middle H that works off one's feeling vent one's spleen
2when S content does not change, the middle cryogenic vulcanization stage finishes, and cure time is 82h.
When start up, arrange sulfuration online, adopt CS
2for vulcanizing agent, adopt inert gas that reaction bed temperature is increased to 215 ℃, then process gas and inert gas are blended together to 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, sulfur-bearing process gas air speed is 1500h
-1, carry out online sulfuration fast; After sulfuration starts, by controlling ratio and the amount of process gas and inert gas, with 70 ~ 100 ℃/h, bed temperature is increased to 350 ℃ fast, controls concentration of hydrogen sulfide in sulfur-bearing process gas and maintain 40 ~ 50g/m
3between; When occurring that hydrogen sulfide penetrates, continue pressure-raising to 2.5 MPa, with 70 ~ 100 ℃/h heating rate, lift temperature to 420 ~ 450 ℃, concentration of hydrogen sulfide maintains 50 ~ 60g/m
3between; When stopping adding vulcanizing agent, 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.At the beginning of 2012, change after sulfur-resistant transformation catalyst, high steam shortage, in the time of cannot heat exchange temperature raising, vulcanizes according to the inventive method.During middle low temperature presulfurization, beds heats up, and temperature reaches after 200 ℃, and 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) enter together with nitrogen the stove that goes into operation and heat in nitrogen; Adopt CS
2as curing medium, vulcanize, vulcanizing agent adopts a small amount of mode repeatedly slowly to add; And by controlling the addition of vulcanizing agent or the heating rate of circulating air temperature control beds at 40 ~ 50 ℃/h, H
2s concentration is at 35 ~ 40g/m
3; Work as H
2s penetrates after beds, slowly strengthens the sulfuration dosage of allocating into, keeps H in recyclegas
2s content is at 56 ~ 60g/m
3, when reaction bed temperature is progressively warming up to 320 ℃, no longer raise; 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; When stopping adding after vulcanizing agent, continuous 3 analysis of catalyst beds middle H that works off one's feeling vent one's spleen
2when S content does not change, the middle cryogenic vulcanization stage finishes, and cure time is 88h.
When start up, arrange sulfuration online, adopt CS
2for vulcanizing agent, adopt inert gas that reaction bed temperature is increased to 200 ℃, then process gas and inert gas are blended together to 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, sulfur-bearing process gas air speed is 400h
-1, carry out online sulfuration fast; After sulfuration starts, by the heating rate of controlling the ratio of process gas and inert gas and measure with 126 ~ 130 ℃/h, bed temperature is increased to 380 ℃ fast, controls concentration of hydrogen sulfide in sulfur-bearing process gas and maintain 65 ~ 70g/m
3between; When occurring that hydrogen sulfide penetrates, continue pressurize at 5.0MPa, with 95 ~ 100 ℃/h heating rate, lift temperature to 445 ~ 450 ℃, concentration of hydrogen sulfide maintains 65 ~ 70g/m
3between; When stopping adding vulcanizing agent, 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.Within 2011, change after sulfur-resistant transformation catalyst, due to electric heater fault, heating power reduces, and according to the inventive method, vulcanizes.During middle cryogenic vulcanization, beds heats up, and temperature reaches after 220 ℃, and 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) enter together with nitrogen the stove that goes into operation and heat in nitrogen; Adopt CS
2as curing medium, vulcanize, vulcanizing agent adopts a small amount of mode repeatedly slowly to add; And by controlling the addition of vulcanizing agent or the heating rate of circulating air temperature control beds at 95 ~ 100 ℃/h, H
2s concentration is at 20 ~ 25g/m
3; Work as H
2s penetrates after beds, slowly strengthens the sulfuration dosage of allocating into, keeps H in recyclegas
2s content is at 40 ~ 43g/m
3, when reaction bed temperature is progressively warming up to 300 ℃, no longer raise; 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; When stopping adding after vulcanizing agent, continuous 3 analysis of catalyst beds middle H that works off one's feeling vent one's spleen
2when S content does not change, the middle cryogenic vulcanization stage finishes, and cure time is 40h.
When start up, arrange sulfuration online, adopt CS
2for vulcanizing agent directly adds in beds, adopt inert gas that reaction bed temperature is increased to 220 ℃, then process gas and inert gas are blended together to 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, sulfur-bearing process gas air speed is 3000h
-1, carry out online sulfuration fast; After sulfuration starts, by controlling ratio and the amount of process gas and inert gas, with 40 ~ 43 ℃/h, bed temperature is increased to 320 ℃ fast, controls concentration of hydrogen sulfide in sulfur-bearing process gas and maintain 40 ~ 50g/m
3between; When occurring that hydrogen sulfide penetrates, continue pressure-raising to 2.5 MPa, with 70 ~ 75 ℃/h heating rate, lift temperature to 400 ~ 405 ℃, concentration of hydrogen sulfide maintains 40 ~ 45g/m
3between; When stopping adding vulcanizing agent, 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.At the beginning of 2012, change after sulfur-resistant transformation catalyst, electric heater fault, in the time of cannot heat exchange temperature raising, vulcanizes according to the inventive method.During middle low temperature presulfurization, beds heats up, and temperature reaches after 212 ℃, and 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) enter together with nitrogen the stove that goes into operation and heat in nitrogen; Adopt CS
2as curing medium, vulcanize, vulcanizing agent adopts a small amount of mode repeatedly slowly to add; And by controlling the addition of vulcanizing agent or the heating rate of circulating air temperature control beds at 60 ~ 65 ℃/h, H
2s concentration is at 32 ~ 36g/m
3; Work as H
2s penetrates after beds, slowly strengthens the sulfuration dosage of allocating into, keeps H in recyclegas
2s content is at 48 ~ 51g/m
3, when reaction bed temperature is progressively warming up to 315 ℃, no longer raise; 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; When stopping adding after vulcanizing agent, continuous 3 analysis of catalyst beds middle H that works off one's feeling vent one's spleen
2when S content does not change, the middle cryogenic vulcanization stage finishes, and cure time is 94h.
When start up, arrange sulfuration online, adopt CS
2for vulcanizing agent drops in process gas, adopt inert gas that reaction bed temperature is increased to 208 ℃, then process gas and inert gas are blended together to 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, sulfur-bearing process gas air speed is 1800h
-1, carry out online sulfuration fast; After sulfuration starts, by controlling ratio and the amount of process gas and inert gas, with 80 ~ 85 ℃/h, bed temperature is increased to 350 ℃ fast, controls concentration of hydrogen sulfide in sulfur-bearing process gas and maintain 40 ~ 50g/m
3between; When occurring that hydrogen sulfide penetrates, continue pressure-raising to 3.0MPa, with 80 ~ 85 ℃/h heating rate, lift temperature to 440 ~ 450 ℃, concentration of hydrogen sulfide maintains 58 ~ 60g/m
3between; When stopping adding vulcanizing agent, 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.At the beginning of 2012, change after sulfur-resistant transformation catalyst, high steam shortage, in the time of cannot heat exchange temperature raising, vulcanizes according to the inventive method.During middle low temperature presulfurization, beds heats up, and temperature reaches after 208 ℃, and 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) enter together with nitrogen the stove that goes into operation and heat in nitrogen; Adopt CS
2as curing medium, vulcanize, vulcanizing agent adopts a small amount of mode repeatedly slowly to add; And by controlling the addition of vulcanizing agent or the heating rate of circulating air temperature control beds at 45 ~ 18 ℃/h, H
2s concentration is at 28 ~ 31g/m
3; Work as H
2s penetrates after beds, slowly strengthens the sulfuration dosage of allocating into, keeps H in recyclegas
2s content is at 35 ~ 38g/m
3, when reaction bed temperature is progressively warming up to 309 ℃, no longer raise; 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; When stopping adding after vulcanizing agent, continuous 3 analysis of catalyst beds middle H that works off one's feeling vent one's spleen
2when S content does not change, the middle cryogenic vulcanization stage finishes, and cure time is 78h.
When start up, arrange sulfuration online, adopt CS
2for vulcanizing agent drops in process gas, adopt inert gas that reaction bed temperature is increased to 213 ℃, then process gas and inert gas are blended together to sulfur-bearing process gas according to the ratio of 2.0:1, control H in process gas
2s content is at 33 ~ 36g/m
3, sulfide stress is 3.5MPa, sulfur-bearing process gas air speed is 1800h
-1, carry out online sulfuration fast; After sulfuration starts, by controlling ratio and the amount of process gas and inert gas, with 78 ~ 85 ℃/h, bed temperature is increased to 360 ℃ fast, controls concentration of hydrogen sulfide in sulfur-bearing process gas and maintain 47 ~ 50g/m
3between; When occurring that hydrogen sulfide penetrates, keep pressure at 3.5 MPa, with 78 ~ 85 ℃/h heating rate, lift temperature to 420 ~ 425 ℃, concentration of hydrogen sulfide maintains 65 ~ 70g/m
3between; When stopping adding vulcanizing agent, 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 within 2008, new equipment goes into operation presulfurization, Co-Mo sulfur-tolerant shift catalyst with embodiment 1 employing same model same amount, adopt traditional vulcanization, process is as follows: when transformation system reaction bed temperature reaches 210 ℃, hydrogen is added to (volume ratio: hydrogen: nitrogen=1:4) enter together with nitrogen the stove that goes into operation and heat in nitrogen, controlling reactor inlet temperature is 200～220 ℃, pressure 0.5MPa left and right, the about 280h of gas circulation air speed
-1, adopt CS
2as curing medium, vulcanize, initial stage entrance concentration of hydrogen sulfide is 5g/m
3, bed temperature rises to 260 ~ 300 ℃, and hydrogen content maintains 20% left and right, according to beds temperature rise situation and concentration of hydrogen sulfide, slowly increases and decreases CS
2and the addition of hydrogen, after 30h, system outlet occurs that hydrogen sulfide penetrates.According to beds temperature rise situation and concentration of hydrogen sulfide, slowly increase and decrease CS
2and the addition of hydrogen, wait to stop adding CS
2, and the continuous outlet hydrogen sulfide contents of analyzing for 3 times continue to improve bed temperature to 300 ~ 350 ℃ when substantially constant, maintain pressure and gas air speed is constant, concentration of hydrogen sulfide is 5 ~ 10g/m
3.When stopping adding CS
2, and the continuous outlet hydrogen sulfide contents of analyzing for 3 times are when substantially constant, according to method above, successively bed temperature are progressively increased to 400 ~ 420 ℃, then suitably improve pressure to 0.8Mpa left and right, stop adding CS
2, continuous 3 analysis outlet hydrogen sulfide contents are substantially constant, are 10g/m
3left and right, sulfuration finishes.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, at the Co-Mo sulfur-tolerant shift catalyst with embodiment 2 employing same model same amounts in 2007, adopts conventional presulfurization mode to carry out catalyst vulcanization, and sulfuration atmospheric pressure is 0.5MPa, air speed 240h-1, and hydrogen sulfide content is 5 ~ 10g/m
3, programming rate is controlled at 30 ~ 40 ℃/h, and sulfidation is with comparative example 1, the about 178h of cure time, after air guide success, the total interconversion rate of transformation system CO reaches 98.1%.
Comparative example 3
Device C described in embodiment 3 was at start up in 2007, and the Co-Mo sulfur-tolerant shift catalyst with embodiment 2 employing same model same amounts, adopts conventional presulfurization mode to carry out catalyst vulcanization, and sulfuration atmospheric pressure is 0.8MPa, air speed 300 h
-1, hydrogen sulfide content is 8 ~ 12g/m
3, programming rate is controlled at 30 ~ 40 ℃/h, and sulfidation is with comparative example 1, the about 85h of cure time, after air guide success, the total interconversion rate of transformation system CO reaches 98.0%.
The above, be only preferred embodiment of the present invention, is not the present invention to be done to the restriction of other form, and any those skilled in the art may utilize the technology contents of above-mentioned announcement to be changed or be modified as the equivalent embodiment of equivalent variations.But every technical solution of the present invention content that do not depart from, any simple modification, equivalent variations and the remodeling above embodiment done 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 sulfur-resistant transformation catalyst substep vulcanization process, is characterized in that, comprises online short vulcanization two steps of middle low-temperature circulating presulfurization and high temperature, and concrete implementing process step is:
1.1, change furnace is heated up, when reaction bed temperature reaches after 200 ~ 220 ℃, 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 be controlled at 1 ~ 25%; Vulcanizing agent adopts a small amount of mode repeatedly slowly to add; And the heating rate of controlling beds by the control addition of vulcanizing agent or the temperature of circulating air is at 40 ~ 100 ℃/h, H
2s concentration is at 20 ~ 40g/m
3; Work as H
2s penetrates after beds, slowly strengthens the sulfuration dosage of allocating into, keeps H in circulating air
2s content is at 40 ~ 60g/m
3, reaction bed temperature is warming up to 300 ~ 320 ℃, till no longer continuing to raise to temperature; 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; When stopping adding after vulcanizing agent, continuous 3 analysis of catalyst beds middle H that works off one's feeling vent one's spleen
2when S content does not change, can be judged as low temperature presulfurization and finish;
1.2, when start up, 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 ℃, again process gas and inert gas are blended together to 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, 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 ℃/h, reaction bed temperature is increased to 320 ~ 380 ℃, directly carries out in catalyst high temperature vulcanizedly, when occurring that hydrogen sulfide penetrates, continue to improve reaction bed temperature to 400 ~ 450 ℃, H
2s content to 40 ~ 70g/m
3, proceed high temperature and vulcanize online; When stopping adding vulcanizing agent, continuous 3 analysis of catalyst beds middle H that works off one's feeling vent one's spleen
2when S content does not change, middle high temperature vulcanizes end online.
2. a kind of sulfur-resistant transformation catalyst substep vulcanization process 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 sulfur-resistant transformation catalyst substep vulcanization process according to claim 1, is characterized in that: the heating rate of beds described in step 1.1 is at 40 ~ 60 ℃/h.
4. a kind of sulfur-resistant transformation catalyst substep vulcanization process according to claim 1, is characterized in that: the heating rate of beds described in step 1.2 is 50 ~ 100 ℃/h.
5. a kind of sulfur-resistant transformation catalyst substep vulcanization process 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 sulfur-resistant transformation catalyst substep vulcanization process 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 sulfur-resistant transformation catalyst substep vulcanization process 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 sulfur-resistant transformation catalyst substep vulcanization process according to claim 1, is characterized in that: described in step 1.2, heating up is nitrogen or argon gas with inert gas.
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| CN106268975A (en) * | 2016-08-30 | 2017-01-04 | 内蒙古博大实地化学有限公司 | Change furnace catalyst low-pressure heater heating process gas vulcanizing equipment and vulcanization process thereof |
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