CN106179524B - A kind of method for pre-sulphuration of CO sulfur-resistant transformation catalysts - Google Patents
A kind of method for pre-sulphuration of CO sulfur-resistant transformation catalysts Download PDFInfo
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- CN106179524B CN106179524B CN201610534013.6A CN201610534013A CN106179524B CN 106179524 B CN106179524 B CN 106179524B CN 201610534013 A CN201610534013 A CN 201610534013A CN 106179524 B CN106179524 B CN 106179524B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/20—Sulfiding
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J33/00—Protection of catalysts, e.g. by coating
Abstract
The invention discloses a kind of CO sulfur-resistant transformation catalysts method for pre-sulphuration; described method is to be handled after CO sulfur-resistant transformation catalysts are vulcanized using passivating technique; catalyst after transpassivation does not need nitrogen protection in storage, transport, filling, is operated in air.The beneficial effects of the invention are as follows：The activity of the CO sulfur-resistant transformation catalysts of presulfurization is substantially better than the activity after vulcanizing in oxidation state CO sulfur-resistant transformation catalysts device；The catalyst of presulfurization only needs to be heated up with nitrogen when in use, and reaching temperature in use can air guide；It is easy to use, reduce obvious production cost, the saving energy, non-environmental-pollution；And the intensity and its strength stability of the catalyst of presulfurization are good；Active high, activity stability is good.
Description
Technical field
The present invention relates to catalyst technical field, more particularly to a kind of method for pre-sulphuration of CO sulfur-resistant transformation catalysts.
Background technology
The CO transformation catalysts used in the world, its development course experienced iron system, copper system and cobalt molybdenum system three generations.Iron system urges
Agent is the catalyst succeeded in developing in the past the 1960s, and operating temperature range is 350-550 DEG C, and CO drops after transformationreation
To about 3%, suitable for without the low transformationreation of sulphur or sulfur content.With the development of desulfurization technology, the sulfur content in synthesis gas can
Below 1ppm is down to, have developed the copper system low temperature conversion catalyst of active high but mithridatism difference, operation temperature the 1960s
200-280 DEG C of degree, CO is down to 0.3% or so after transformationreation.With the change of energy resource structure, the raw material for producing synthesis gas is changed into
Heavy oil, residual oil and coal grade height sulfur material.The Co-Mo sulfur-tolerant shift catalyst that later stage the 1960s develops can be used for direct
Convert sulfur-bearing synthesis gas, and active wide temperature region, the advantages that light-off temperature is low, and shift activity is high.
Co-Mo sulfur-tolerant shift catalyst is developed by foreign countries earliest.The K8-11 of BASF Corp. of Germany in 1969 takes the lead in
Succeed in developing, be characterized in using magnesium aluminate spinel as carrier, activity is high, and antitoxin thing ability is strong.Afterwards, Top of Denmark rope company
SSK catalyst, the C113 catalyst of UBE Industries Ltd., C25-2-02 catalyst of UCI companies of the U.S. etc. are successive
Succeed in developing.
Domestic sulfur-resistant transformation catalyst research and development quickly, from the last century 80's so far, emerges different company
Multiple brands sulfur-resistant transformation catalyst.The indices of domestic sulfur-resistant transformation catalyst have reached international standards.
Succeed in developing the sixties in last century and obtain the Co-Mo sulfur-tolerant shift catalyst of wide application in recent two decades,
Due to compared with conventional Fe-Cr HTS transformation catalyst and copper system low temperature conversion catalyst, having using wide temperature region, shift activity
Height, in the absence of sulfur poisoning problem, thus it is in widespread attention.
The Co-Mo sulfur-tolerant shift catalyst of industry is typically using the oxide of cobalt and molybdenum as active constituent, with oxidation at present
Aluminium, magnesia are carrier, although its shift activity is good, to air speed, water/gas than adaptability it is wide, can preferably be applied to
The needs of existing coal chemical engineering equipment.But such catalyst, which has to pass through vulcanization, can just make catalyst have shift activity, be adopted
Vulcanization is sulfurization technology in conventional device, i.e., after Catalyst packing, sulphur is circulated by process gas vulcanization or vulcanizing agent
Change.
In existing device there are problems in sulfurization technology, main as follows：
1st, presulfiding of catalyst initial stage, because bed bottom is without sulphur, it is nonactive phase to cause active component partial reduction, from
And reduce catalytic activity；
2nd, vulcanization is unstable in device；
3rd, vulcanization investment is big in device（There is supporting individually elevated temperature cure system and sulfidation consumes substantial amounts of manpower
Physical resources and financial resources）, environmental pollution, potential safety hazard are big（Vulcanizing agent used is poisonous, flammable and explosive substance in sulfidation, peace
Full hidden danger is big）；
4th, vulcanisation operation control is difficult in device；
5th, vulcanization on-stream time length in device, wastes a large amount of process gas；
6th, vulcanization state of cure (vulcanization) is low in device, reduces catalytic activity and service life.
The presence of problem above, the development to sulphur-resistant conversion bring certain difficulty, and model is applied if thinking further to expand
Enclose, increase economic efficiency, develop corresponding ex situ presulfiding technology and be very important.
In Chinese patent CN100469449C, pretreating agent of the sulfur-resistant transformation catalyst with sulfur-bearing agent outside device is connect
Touch, vulcanizing agent is entered in catalyst gap, and carry out Passivation Treatment.The presulfurization sulfur-resistant transformation catalyst category that the method obtains
Still need hydrogen when load sulfur type catalyst, use and carry out reversion, not pre-sulfide catalyst truly.In
In state patent CN105233881A, sulfur-resistant transformation catalyst carries out the outer sulfuration process of device using deep cooling passivation preconditioning technique, adopts
It is passivated with supplying air, loads in hermetic bag and vacuumize preservation.Although catalytic inner sulfurate activity center is unaffected,
But catalyst coating sulphur center is oxidized to sulfuric acid state, and stores and need to be sealed in transportation, loaded
Inert gas shielding is also required in journey.In Chinese patent CN105233867A, sulfur-resistant transformation catalyst uses high-molecular compound
The outer wrap thing of formation is protected to sulphided state catalyst, although realizing the ex situ presulfiding of catalyst, during film forming
Between it is long, condition is harsh, and can not ensure catalyst parcel it is uniform fully wrapped around, storage, transport, filling during vibrations
Easily cause integument to come off with broken, make sulfurate activity center and air contact and be oxidized.
In summary, at present, Co-Mo sulfur-tolerant shift catalyst can not carry out effectively ex situ presulfiding, vulcanize outside device
Cost is very high, leads to not normal production and promotes.Main reasons is that the active component of the catalyst is sulphided state, and sulphur
The catalyst for changing state is the porous particle of high-specific surface area, has oxytropism, is chronically exposed to unstable in air, chance oxygen meeting
Sulfur dioxide and heat release are produced, there is self-heating or the trend of burning below 200 DEG C.
The content of the invention
In order to meet the needs of vulcanizing outside CO sulfur-resistant transformation catalysts device, the invention provides a kind of catalysis of CO sulphur-resistant conversions
The method for pre-sulphuration of agent.A kind of succinct, efficient, convenient ex situ presulfiding method, the CO sulphur-resistant conversions catalysis of presulfurization are provided
Agent can for a long time store, transports, load operation in an atmosphere.
, will the invention provides a kind of method for pre-sulphuration of CO sulfur-resistant transformation catalysts in order to realize foregoing invention purpose
CO sulfur-resistant transformation catalysts and sulphur mixing load first vulcanization plant, in pressure P1Under, nitrogen is filled with, and be warming up to certain
Temperature T1, then stop inflated with nitrogen, switch hydrogen and be pressurized to pressure P with hydrogen2, then stop being filled with hydrogen, control certain
Heating rate is warming up to temperature T2Afterwards, continue after vulcanizing a period of time t, to the end of vulcanization, with nitrogen by first vulcanization plant
Interior gas, which is blown into second and is fitted into the vulcanization plant of CO sulfur-resistant transformation catalysts and sulphur, to be recycled, first vulcanization dress
It is filled with temperature adjustment to T in putting after nitrogen displacement3, then add passivator and be passivated, be passivated after terminating in nitrogen
Atmosphere drops to 0-30 DEG C.
The T1 ≤T2, T3<T2, the pressure P1For 0-1.0MPa；The pressure P2For 0-1.0MPa；The temperature T1
For 150-350 DEG C；The temperature T of vulcanization2For 150-450 DEG C, the temperature T3For 0-300 DEG C.
The pressure P2For 0.2-0.5MPa；The temperature T1For 180-230 DEG C；The temperature T of vulcanization2For 200-350
DEG C, the temperature T3For 30-150 DEG C.
The t is 2-4h.
It is one kind in ethylene glycol, Propanolamine, butanol, propyl alcohol that the passivator, which contains component A and component B, the component A,
Or a variety of mixtures, the component B are one or more mixtures in urea, glycerine, acrylamide.
The component A:Component B mass ratioes are 1-2: 3-5.
The addition of the passivator is the 5-8% of CO sulfur-resistant transformation catalyst quality.
The CO sulfur-resistant transformation catalysts and sulphur mass ratio are 100: 1-100: 20.
The CO sulfur-resistant transformation catalysts and vulcanizing agent mass ratio are 100: 3-100: 12.
By adopting the above-described technical solution, overcoming initial vulcanization step in catalyst device, because bed bottom is without sulphur, cause
Active component partial reduction is nonactive phase, so as to reduce catalytic activity；And vulcanization is unstable in device；Vulcanization investment is big,
Environmental pollution is big, potential safety hazard is big；Vulcanisation operation control hardly possible, on-stream time length, waste a large amount of process gas in device；Vulcanization sulphur in device
Change degree is low, the deficiencies of reducing catalytic activity and service life etc..Catalyst through over cure uses passivating technique, and process is blunt
Catalyst after change does not need nitrogen protection in storage, transport, filling, is operated in air.This technical scheme presulfurization
The activity of sulfur-resistant transformation catalyst is substantially better than sulfurate activity in oxidation state sulfur-resistant transformation catalyst device；The catalyst of presulfurization exists
Only need to be heated up with nitrogen during use, reaching temperature in use can air guide.It is easy to use, it is bright to reduce production cost
Aobvious, the saving energy, non-environmental-pollution；And the intensity and its strength stability of the catalyst of presulfurization are good；Active high, activity is steady
It is qualitative good.
The beneficial effect of ex situ presulfiding technology of the present invention is that fundamentally solve the sulphur-resistant conversion catalysis of vulcanization in device
The problem of agent exists when vulcanizing.Have the following advantages that compared with prior art：
1st, catalyst performance is improved.Catalyst vulcanization is more abundant, and it is low activity gold to avoid active component by hot hydrogen reduction
The possibility of category, so as to substantially increase the utilization rate of active component and catalytic activity, prepared by activity and the traditional handicraft of catalyst
Catalyst compared to improve more than 10%.Active component is utilized to greatest extent, improves stability, and extending catalyst makes
Use the life-span.Pre-sulfide catalyst has higher mechanical strength and strength stability.
2nd, catalyst goes into operation simplicity, saves time and fund.Without vulcanization, need to be to temperature in use with nitrogen temperature only
Can.On-stream time greatly shortens 2/3, it is not necessary to single curing system, reduces construction investment.
3rd, be advantageous to environmental protection, avoid H2、CS2Etc. the use of inflammable and explosive gas and poisonous vulcanizing agent, reduce
Environmental pollution.
4th, the stability that converting means is driven is improved.
Embodiment
It is high for the cost that vulcanizes outside current device, vulcanize the problem of can not being effectively passivated outside device, the present invention provides a kind of
Succinctly, efficiently, the method for pre-sulphuration of the outer CO sulfur-resistant transformation catalysts of convenient device.CO sulfur-resistant transformation catalyst energy after presulfurization
Enough storages long-term in an atmosphere, transport, filling operation.
Comparative example 1
Take the ripe cobalt molybdenum system CO sulfur-resistant transformation catalysts KC-103 of commercial Application（Oxidation state）, it is designated as sample A.
Embodiment 1
By 1kg industry cobalt molybdenum system CO sulfur-resistant transformation catalysts KC-103（Oxidation state）And sulphur（30g）Mixing loads first
Individual vulcanization plant, in P1Under=0.1MPa pressure, nitrogen is filled with, and is warming up to certain temperature T1=180 DEG C, then stop inflated with nitrogen
Switch hydrogen and with hydrogen punching press to pressure P2=0.2MPa, then stop be filled with hydrogen, then control heating rate be 35 DEG C/
H, it is warming up to T2Continue after=250 DEG C after vulcanizing a period of time t=2h, to the end of vulcanization, with nitrogen by first vulcanization plant
Gas be blown into second and be fitted into the vulcanization plant of Co-Mo sulfur-tolerant shift catalyst and sulphur and recycle, first vulcanization
It is filled with temperature adjustment to T in device after nitrogen displacement3=30 DEG C, then add passivator and be passivated, after passivation terminates
15 DEG C are down under nitrogen atmosphere.Catalyst after presulfurization is designated as sample B.
Passivating agent composition A is ethylene glycol, and component B is urea, and ethylene glycol, urea quality ratio are 2: 5.The addition of passivator
Measure 70g.
Co-Mo sulfur-tolerant shift catalyst and sulphur mass ratio are 100: 3.
Embodiment 2
By 1kg industry co-mo antisulphuric transforming catalysts KC-103（Oxidation state）And sulphur（60g）Mixing loads first sulphur
Makeup is put, in P1Under=0.1MPa pressure, nitrogen is filled with, and is warming up to certain temperature T1=205 DEG C, then stop inflated with nitrogen switching
Hydrogen and with hydrogen punching press to pressure P2=0.3MPa, then stop being filled with hydrogen, it is 35 DEG C/h then to control heating rate, is risen
Temperature is to T2Continue after=200 DEG C after vulcanizing a period of time t=2h, to the end of vulcanization, with nitrogen by the gas in first vulcanization plant
Body, which is blown into second and is fitted into the vulcanization plant of Co-Mo sulfur-tolerant shift catalyst and sulphur, to be recycled, first vulcanization plant
In be filled with temperature adjustment to T after nitrogen displacement3=60 DEG C, then add passivator and be passivated, be passivated after terminating in nitrogen
Atmosphere, which is enclosed, drops to 25 DEG C.Catalyst after presulfurization is designated as sample C.
Passivating agent composition A is ethylene glycol, and component B is glycerine, and ethylene glycol, qualities of glycerin ratio are 2: 5.The addition of passivator
Measure 70g.
Co-Mo sulfur-tolerant shift catalyst and sulphur mass ratio are 100: 6.
Embodiment 3
By 1kg industry co-mo antisulphuric transforming catalysts KC-103（Oxidation state）And sulphur（90g）Mixing loads first sulphur
Makeup is put, in P1Under=0.1MPa pressure, nitrogen is filled with, and is warming up to certain temperature T1=205 DEG C, then stop inflated with nitrogen switching
Hydrogen and with hydrogen punching press to pressure P2=0.4MPa, then stop being filled with hydrogen, it is 35 DEG C/h then to control heating rate, is risen
Temperature is to T2Continue after=300 DEG C after vulcanizing a period of time t=2h, to the end of vulcanization, with nitrogen by the gas in first vulcanization plant
Body, which is blown into second and is fitted into the vulcanization plant of Co-Mo sulfur-tolerant shift catalyst and sulphur, to be recycled, first vulcanization plant
In be filled with temperature adjustment to T after nitrogen displacement3=100 DEG C, then add passivator and be passivated, be passivated after terminating
Nitrogen atmosphere drops to 25 DEG C.Catalyst after presulfurization is designated as sample D.
Passivating agent composition A is ethylene glycol, and component B is acrylamide, ethylene glycol, the proportion of acylamide 2: 5.Passivation
The addition 70g of agent.
Co-Mo sulfur-tolerant shift catalyst and sulphur mass ratio are 100: 9.
Embodiment 4
By 1kg industry co-mo antisulphuric transforming catalysts KC-103（Oxidation state）And sulphur（120g）Mixing loads first sulphur
Makeup is put, in P1Under=0.1MPa pressure, nitrogen is filled with, and is warming up to temperature T1=230 DEG C, then stop inflated with nitrogen switching hydrogen
And with hydrogen punching press to pressure P2=0.5MPa, then stop being filled with hydrogen, it is 35 DEG C/h then to control heating rate, is warming up to T2
After=350 DEG C, continue after vulcanizing a period of time t=2h, to the end of vulcanization, be blown into the gas in first vulcanization plant with nitrogen
Second is fitted into the vulcanization plant of cobalt molybdenum system CO sulfur-resistant transformation catalysts and sulphur and recycles, and is filled in first vulcanization plant
Enter temperature adjustment to T after nitrogen displacement3=150 DEG C, then add passivator and be passivated, be passivated after terminating in nitrogen
Atmosphere drops to 25 DEG C.Catalyst after presulfurization is designated as sample E.
Passivating agent composition A is Propanolamine, butanol, propyl alcohol mass ratio are 1: 5:2 mixture, component B are glycerine and third
Acrylamide mass ratio is 1:1 mixture, component A:Component B mass ratioes are 2: 3.The addition 70g of passivator.
Co-Mo sulfur-tolerant shift catalyst and sulphur mass ratio are 100: 12.
Embodiment 5
Sulfur consumption in embodiment 1 is changed to 130g.
It is 0.5 that passivating agent composition A, which is changed to ethylene glycol, Propanolamine, butanol, propyl alcohol mass ratio,: 1: 5:2 mixture, group
B is divided to be changed to urea, glycerine and the proportion of acylamide as 1: 1:1 mixture, component A:Component B mass ratioes are 1: 3.It is blunt
The addition 80g of agent.
Co-Mo sulfur-tolerant shift catalyst and sulphur mass ratio are 100: 13.Other conditions are constant, obtained catalyst note
For sample F.
Embodiment 6
Sulfur consumption in embodiment 1 is changed to 20g, other conditions are constant, and obtained catalyst is designated as sample G.
The mass ratio of Co-Mo sulfur-tolerant shift catalyst and sulphur is 100: 2.
Embodiment 7
Sulfur consumption in embodiment 1 is changed to 200g, P1It is changed to 1.0MPa, hydrogen stamping pressure P2It is changed to 0.6MPa, T1
150 DEG C are changed to, T2It is changed to 150 DEG C.
Passivating agent composition A is changed to Propanolamine, butanol mass ratio is 1:3 mixture, component B are changed to urea and acryloyl
Amine mass ratio is 1:2 mixture, component A:Component B mass ratioes are 1: 4.The addition 50g of passivator.
Co-Mo sulfur-tolerant shift catalyst and sulphur mass ratio are 100:20, other conditions are constant, obtained catalyst note
For sample H.
Embodiment 8
By the hydrogen stamping pressure P in embodiment 12It is changed to 0.1MPa, T1350 DEG C are changed to, T2450 DEG C are changed to, other conditions
Constant, obtained catalyst is designated as sample I.
Embodiment 9
By the hydrogen stamping pressure P in embodiment 121.0MPa is changed to, the desired value of inflated with nitrogen heating is changed to T1=165 DEG C,
The time t for continuing vulcanization after heating is changed to 4h, and other conditions are constant, and obtained catalyst is designated as sample J.
Embodiment 10
The desired value T that inflated with nitrogen in embodiment 1 is heated up1245 DEG C are changed to, other conditions are constant, obtained catalyst
It is designated as sample K.
Embodiment 11
The desired value T that will be heated up after the logical hydrogen of stopping in embodiment 12290 DEG C are changed to, other conditions are constant, obtain
Catalyst is designated as sample L.
Embodiment 12
The desired value T that will be heated up after the logical hydrogen of stopping in embodiment 12450 DEG C are changed to, other conditions are constant, obtain
Catalyst is designated as sample M.
Embodiment 13
It will be filled with temperature adjustment to T in first vulcanization plant in embodiment 1 after nitrogen displacement3=27.5 DEG C,
Other conditions are constant, and obtained catalyst is designated as sample N.
Embodiment 14
It will be filled with temperature adjustment to T in first vulcanization plant in embodiment 12 after nitrogen displacement3=175 DEG C,
Other conditions are constant, and obtained catalyst is designated as sample O.
In the embodiment of the present invention, it is 35 DEG C/h to control heating rate, and this heating rate can take 10-60 DEG C/h, be limited to a piece
Width is no longer enumerated.
Catalyst performance evaluation
Unstripped gas composition is represented with percentage by volume：
CO 45-49%, CO25-10%, H2S>0.03%, remaining is hydrogen.
The former granularity assessment device appreciation condition that pressurizes is：
Oxidation state sulfur-resistant transformation catalyst curing temperature is 260 DEG C, cure time 3h；
Catalyst grain size：φ4×(8-15)mm；H2O/ dry gas：1.46（Mol ratio）；
H2S concentration：3000-5000ppm；Pressure：6.0MPa；
Dry gas air speed：3000h-1；Transformation temperature： 265℃、350℃、450℃.
Catalyst stability measure is carried out on the former granularity assessment device of pressurization, appreciation condition：
Pressure：8.0MPa；Temperature：500℃；
H2O/N2：1.6（Mol ratio）；Time：20h；
The activity of catalyst is represented with CO interconversion rates：
XCO=(YCO-Y’CO)/[YCO ×(1+Y’CO)]×100%
Wherein, entrance CO concentration（YCO）With outlet CO concentration（Y’CO）Be butt molar concentration.
The catalyst sample A-O that comparative example and embodiment obtain is carried out to the survey of stability and pressurized shift activity respectively
It is fixed, it is specifically shown in Tables 1 and 2.
The catalyst stability measurement result of table 1
* activity is the pressurization CO interconversion rates under the conditions of 450 DEG C.
Table 1 gives the result that catalyst stability is determined on laboratory original granularity assessment device.Contrast is respectively urged
Agent uses forward and backward intensity and activity preservation rate, shows that the catalyst strength stability of the present invention and activity stability are excellent
In industrial catalyst KC-103.
The catalyst pressurized shift determination of activity result of table 2
Note：Interconversion rate refers to CO interconversion rates X in tableCO。
Table 2 is given on the pressurization original granularity assessment device in laboratory, to ex situ presulfiding catalyst sample and industry
Shift activity comparative evaluation's result that oxidized catalyst KC-103 is carried out.As a result show：The ex situ presulfiding catalysis of the present invention
For agent shift activity compared with oxidation state industrial catalyst KC-103, activity improves more than 10%.
Active component is utilized to greatest extent, improves stability, extends catalyst service life；Presulfurization is catalyzed
Agent has higher mechanical strength and strength stability；Catalyst go into operation it is easier with skimming more catalyst changeout, save the time and
Fund, without vulcanization, only it need to greatly shorten 2/3 with nitrogen temperature to temperature in use, on-stream time, it is not necessary to single sulphur
Change system, construction investment is reduced, and be advantageous to environmental protection, reduce enterprise's carbon emission.Avoid H2、CS2Etc. inflammable and explosive
The use of gas and poisonous vulcanizing agent, reduces environmental pollution；Improve the stability that converting means is driven.
The foregoing is only presently preferred embodiments of the present invention, be not intended to limit the invention, it is all the present invention spirit and
Within principle, any modification, equivalent substitution and improvements made etc., it should be included in the scope of the protection.
Claims (6)
- A kind of 1. ex situ presulfiding method of CO sulfur-resistant transformation catalysts, it is characterised in that by CO sulfur-resistant transformation catalysts and sulphur Sulphur mixing loads first vulcanization plant, in pressure P1Under, nitrogen is filled with, and be warming up to certain temperature T1, then stop nitrogen charging Gas, switch hydrogen and be pressurized to pressure P with hydrogen2, then stop being filled with hydrogen, control certain heating rate to be warming up to temperature T2Afterwards, continue after vulcanizing a period of time t, to the end of vulcanization, the gas in first vulcanization plant is blown into second with nitrogen It is fitted into the vulcanization plant of CO sulfur-resistant transformation catalysts and sulphur and recycles, it is complete to be filled with nitrogen displacement in first vulcanization plant By temperature adjustment to T after finishing3, then add passivator and be passivated, passivation is down to 0-30 DEG C i.e. under nitrogen atmosphere after terminating Can；The T1 ≤T2, T3<T2, the pressure P1For 0-1.0MPa；The pressure P2For 0.2-0.5MPa；The temperature T1For 180-230℃；The temperature T of vulcanization2For 200-350 DEG C, the temperature T3For 30-150 DEG C；The t is 2-4h.
- 2. the ex situ presulfiding method of CO sulfur-resistant transformation catalysts according to claim 1, it is characterised in that the passivation It is one or more mixtures in ethylene glycol, Propanolamine, butanol, propyl alcohol that agent, which contains component A and component B, the component A, The component B is one or more mixtures in urea, glycerine, acrylamide.
- 3. the ex situ presulfiding method of CO sulfur-resistant transformation catalysts according to claim 2, it is characterised in that the component A：Component B mass ratioes are 1-2: 3-5.
- 4. according to the ex situ presulfiding method of any described CO sulfur-resistant transformation catalysts of claim 1-3, it is characterised in that institute The addition for stating passivator is the 5-8% of CO sulfur-resistant transformation catalyst quality.
- 5. according to the ex situ presulfiding method of any described CO sulfur-resistant transformation catalysts of claim 1-3, it is characterised in that institute It is 100 to state CO sulfur-resistant transformation catalysts and sulphur mass ratio: 1-100: 20.
- 6. the ex situ presulfiding method of CO sulfur-resistant transformation catalysts according to claim 5, it is characterised in that the CO is resistance to Sulfur change catalyst and sulphur mass ratio are 100: 3-100: 12.
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