CN103769116A - Sulfur tolerant shift catalyst and preparation method - Google Patents
Sulfur tolerant shift catalyst and preparation method Download PDFInfo
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- CN103769116A CN103769116A CN201210402772.9A CN201210402772A CN103769116A CN 103769116 A CN103769116 A CN 103769116A CN 201210402772 A CN201210402772 A CN 201210402772A CN 103769116 A CN103769116 A CN 103769116A
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Abstract
The invention relates to a sulfur tolerant shift catalyst and a preparation method. The sulfur tolerant shift catalyst employs Co and Mo as active components and does not contain potassium and rare earth compounds, and the carrier employs heat-treatment modified attapulgite clay instead of a conventional magnesium aluminium material. During preparation, natural attapulgite clay is subjected to heat treatment instead of acid processing, so that the processing for a waste acid solution is avoided; by employing a mixing-kneading method for preparation, the active compositions are dispersed uniformly and not easy to lose, and the activity stability of the catalyst is increased; and compared with an immersing method of the prior art, the water usage amount for preparation is saved, also the preparation process and the operation process are simplified, and the cost advantage is obvious. The catalyst has relatively high strength, a proper pore structure, good anti-hydration performance and stability, is suitable for shift technological conditions such as middle-high pressure, high space velocity, high water-gas ratio, middle-high temperature and the like, is capable of satisfying requirements of shift workshop sections in novel coal chemical industry on shift catalysts, and has good popularization and application value.
Description
Technical field
The invention belongs to Coal Chemical Industry sulphur-resistant conversion technical field, be specifically related to a kind of sulfur-resistant transformation catalyst and preparation method.
Background technology
Water gas shift/WGS is one of industrial critical process such as synthetic ammonia, synthesizing methanol and hydrogen manufacturing, and in this process, high activity, high stability transformation catalyst play an important role.Wherein, suitable temperature range is wide, shift activity is high because having for Co-Mo sulfur-tolerant shift catalyst, resistance to sulphur and the feature such as anti-poisoning performance is good, and the commercial Application achievement in conversion process is particularly outstanding.This type of catalyst generally adopts coprecipitation, kneading method or infusion process to make, and its active component is generally selected from VIII family and the group vib metallic compound take cobalt and molybdenum as representative, and auxiliary agent is generally selected from alkali metal, alkaline-earth metal and rare earth compound etc.Its carrier component is generally selected from the raw material of industry of elements such as containing Mg, Al, Ti.
Natural attapulgite clay claims again palygorskite, is a kind of clay mineral take attapulgite as key component.Attapulgite is the layer chain silicate mineral of a kind of crystalloid containing Shuifu County's magnalium, and the theoretical chemistry formula of concave convex rod crystal is Mg
5si
8o
20(OH)
2(OH
2)
44H
2o.Attapulgite has the performances such as unique high temperature resistant, anti-saline and alkaline, adsorption bleaching, and there is good plasticity and cohesive force, be widely used as the materials such as drier, adsorbent and catalyst carrier in fields such as building materials, environmental protection, chemical industry, enjoy the good reputation of " kings of thousand soil ", " soil of general-purpose ".China's attapulgite clay reserves account for the more than 70% of global reserves, but it utilizes still more in the extensive style exploitation process segment.Mainly for the production of lower primary product of technology content such as exterior coating, compound fertilizer binding agent and feed addictives, product lacks scientific and technological content, and added value is on the low side, and price is comparatively cheap.Along with deepening continuously that attapulgite clay is developed, set it as carrier material cheap and easy to get and shown good catalytic performance for the preparation of sulfur-resistant transformation catalyst, also for the deep processing utilization of attapulgite clay provides effective way.Therefore, attapulgite clay is more and more paid close attention in the application of catalytic field in recent years.
Chinese patent CN102198401A relates to a kind of attapulgite clay that adopts and prepares cobalt molybdenum CO sulfur-resistant transformation catalyst and method thereof as carrier, and applies it in CO transformationreation.The method that adopts dipping-precipitation by the oxide of nanoscale or its salt dopping in the attapulgite clay of acid treatment, preparation respective carrier, flooding afterwards cobalt active component of cobalt, to prepare cobalt molybdenum be CO sulfur-resistant transformation catalyst.Recessed native carrier is with respect to commercial active carbon, γ-Al
2o
3, MgAl
2o
4cheap in carrier, there is larger commercial Application meaning, but method water consumption described in this invention is large, containing sour water difficult treatment, preparation section complexity.
Summary of the invention
The object of the invention is to provide a kind of sulfur-resistant transformation catalyst and preparation method, after this catalyst employing attapulgite clay heat treatment, as the carrier component of catalyst, has reduced preparation cost, avoids the processing to acid pickle; Have that intensity is high, pore volume and specific surface is suitable, hydration-resisting performance and having good stability, met the requirement of conversion section to transformation catalyst in New Coal Chemical.
Sulfur-resistant transformation catalyst of the present invention, comprise carrier and active component, its be using the attapulgite clay after heat treatment modification add containing the powdered compounds of magnesium, containing the powdered compounds of aluminium and the powdered compounds of titaniferous as carrier, using Co, Mo binary composition as active component.
Sulfur-resistant transformation catalyst of the present invention, its chemical composition is by percentage to the quality:
Cobalt compound, in CoO, content is 1.0～4.5%;
Molybdate compound, with MoO
3meter, content is 5.0～10.0%;
Magnesium-containing compound, in MgO, content is 10.0～17.0%;
Aluminum contained compound, with Al
2o
3meter, content is 30.0～43.5%;
Titanium-containing compound, with TiO
2meter, content is 14.5～20.0%;
Surplus is the attapulgite clay of heat treatment modification.
In described heat treatment modified attapulgite clay, magnesia, silica and aluminium oxide total content are higher than 75%.
The preparation method of sulfur-resistant transformation catalyst of the present invention, catalyst adopts kneading method preparation, and active component, support material, pore creating material mix with binding agent, and moulding, dry, roasting, make finished catalyst, comprises the steps:
1. prepare heat treatment modified attapulgite clay:
Adopt the mode of roasting to prepare heat treatment modified attapulgite clay, sintering temperature is 400～600 ℃, roasting time is 2～8h, then carry out the above granularity content of pulverization process to 240 order and be not less than 90%, obtain heat treatment modified attapulgite clay, contained magnesia, silica and aluminium oxide total content are higher than 75%;
2. the preparation of active component solution:
By molybdate compound deionized water dissolving, obtain solution A; By cobalt compound deionized water dissolving, then binding agent is added wherein, stirring and dissolving, obtains solution B;
3. shaping of catalyst:
The attapulgite clay of heat treatment modification with powdered compounds containing the powdered compounds of magnesium, titaniferous, mix containing powdered compounds and the pore creating material of aluminium, is added to solution A, mediate evenly; Add again solution B, mediate evenly extruded moulding;
4. dry:
Catalyst after moulding is at room temperature placed 24～48h and is naturally dried;
5. roasting:
Dried catalyst carries out calcination process, and temperature-rise period adopts the mode of gradient increased temperature, and 20 ℃ are warming up to 200 ℃ through 1h, constant temperature 1h at 200 ℃, then be warming up to required sintering temperature through 1h, and sintering temperature is 400～600 ℃, roasting time is 2～8h.
Described cobalt compound is selected from cobalt nitrate or cobalt acetate, preferably cobalt nitrate.
Described molybdate compound is selected from ammonium molybdate.
The described powdered compounds containing magnesium is selected from magnesia, magnesium oxalate, magnesium carbonate or dolomol, preferential oxidation magnesium.
The described powdered compounds containing aluminium is selected from boehmite, aluminium glue or aluminium oxide, preferably boehmite.
The powdered compounds of described titaniferous is selected from metatitanic acid, titanium oxide or anatase, preferably metatitanic acid.
Described pore creating material is selected from polyvinyl alcohol, poly amic acid, field mountain valley with clumps of trees and bamboo powder, citric acid, starch or sucrose, preferably sesbania powder, and the addition in preparation process is 1～8% of catalyst end product quality, preferably 2～4%;
Described binding agent is selected from one or more in water, acetic acid, citric acid, oxalic acid or nitric acid, optimization citric acid and/or oxalic acid, and the addition in preparation process is 1～8% of catalyst end product quality, preferably 2～4%.Binding agent and main body catalytic component compatibility are good, guarantee that catalyst has higher intensity and good stability.
Described sulfur-resistant transformation catalyst technical indicator:
Catalyst appearance bar shaped
Appearance and size diameter phi 3.5～4.0mm
Specific surface 100～160m
2g
-1, preferably 120～140m
2g
-1
Pore volume 0.2～0.5cm
3g
-1, preferably 0.25～0.40cm
3g
-1
Compared with prior art, beneficial effect of the present invention is as follows:
Sulfur-resistant transformation catalyst of the present invention has higher intensity, suitable pore structure, good hydration-resisting performance and stability, be applicable to the conversion process conditions such as mesohigh, high-speed, high WGR, middle high temperature, can meet the requirement of conversion section to transformation catalyst in New Coal Chemical.
This catalyst adopts wide material sources, attapulgite clay part with low cost to substitute magnalium material, has reduced catalyst preparation cost; This catalyst adopts heat treatment mode to replace acid treatment mode to natural attapulgite clay, has avoided the processing to acid pickle; This catalyst adopts kneading method preparation, active component is uniformly dispersed in carrier, be difficult for running off, increase the activity stability of catalyst, compared with the infusion process of prior art, both saved preparation water consumption, simplify again preparation process and operational sequence, cost advantage is remarkable, has good economic benefit and popularizing application prospect.
Accompanying drawing explanation
Fig. 1 is the present invention's activity rating apparatus structure schematic diagram that pressurizes;
In figure: 1, raw material gas purifying device; 2, pressure reducer; 3, blender; 4, Pressure gauge; 5, lockout valve; 6, heating furnace; 7, reaction tube; 8, thermocouples tube in pipe; 9, condenser; 10, separator; 11, drain pump; 12, wet flow indicator; 13, vaporizer; 14, tank; 15, water measuring pump.
The specific embodiment
Below in conjunction with embodiment, the present invention is described further.
Embodiment 1
First, by attapulgite clay roasting 3h at 600 ℃, then pulverize 240 mesh sieves, obtained heat treated attapulgite clay.10.5g ammonium molybdate is dissolved in 40.0mL deionized water, obtains ammonium molybdate solution A; 13.6g cobalt nitrate is dissolved in 30.0mL deionized water, then 3.0g citric acid and 3.0g oxalic acid are joined in above-mentioned cobalt nitrate solution successively, stirring and dissolving, obtains the solution B containing cobalt.
Take the heat treated attapulgite clay of 18.8g, 15.0g magnesia, 54.6g boehmite, 20.0g metatitanic acid, 3.0g sesbania powder and mix, add solution A, mediate evenly; Add solution B, kneading, moulding, dry naturally, then roasting again, and temperature-rise period adopts the mode of gradient increased temperature, and 20 ℃ are warming up to 200 ℃ through 1h, constant temperature 1h at 200 ℃, then be warming up to 500 ℃ through 1h, roasting 4h, is down to room temperature naturally.
Obtain sulfur-resistant transformation catalyst C-1.Its intensity, pore structure and pressurization activity data thereof are in table 1,2.
First by attapulgite clay at 580 ℃ of roasting temperature 3h, then pulverized 240 mesh sieves, obtain heat treated attapulgite clay.6.2g ammonium molybdate is dissolved in 35.0mL deionized water, obtains ammonium molybdate solution A; 3.9g cobalt nitrate is dissolved in 35.0mL deionized water, then 5.0g citric acid is joined in above-mentioned cobalt nitrate solution, stirring and dissolving, obtains the solution B containing cobalt.
Take 40.0g attapulgite clay, 36.8g magnesium oxalate, 42.9g boehmite, 17.5g metatitanic acid, 3.0g sesbania powder and mix, add solution A, mediate evenly; Add solution B, kneading, moulding, dry naturally, then roasting again, and temperature-rise period adopts the mode of gradient increased temperature, and 20 ℃ are warming up to 200 ℃ through 1h, constant temperature 1h at 200 ℃, then be warming up to 530 ℃ through 1h, roasting 3h, is down to room temperature naturally.
Obtain sulfur-resistant transformation catalyst C-2.Its intensity, pore structure and pressurization activity data thereof are in table 1,2.
First by attapulgite clay at 550 ℃ of roasting temperature 3h, then pulverized 240 mesh sieves, obtain heat treated attapulgite clay.12.3g ammonium molybdate is dissolved in 40.0mL deionized water, obtains ammonium molybdate solution A; 17.5g cobalt nitrate is dissolved in 30.0mL deionized water, then 3.0g citric acid is joined in above-mentioned cobalt nitrate solution, stirring and dissolving, obtains the solution B containing cobalt.
Take 5.0g attapulgite clay, 60.0g magnesium acetate, 42.9g boehmite, 6.0g metatitanic acid, 3.0g sesbania powder and mix, add solution A, mediate evenly; Add solution B, kneading, moulding, dry naturally, then roasting again, and temperature-rise period adopts the mode of gradient increased temperature, and 20 ℃ are warming up to 200 ℃ through 1h, constant temperature 1h at 200 ℃, then be warming up to 550 ℃ through 1h, roasting 2h, is then cooled to room temperature naturally.
Obtain finished product sulfur-resistant transformation catalyst C-3.Its intensity, pore structure and pressurization activity data thereof are in table 1,2.
First by attapulgite clay at 500 ℃ of roasting temperature 3h, then pulverized 240 mesh sieves, obtain heat treated attapulgite clay.8.0g ammonium molybdate is dissolved in 40.0mL deionized water, obtains ammonium molybdate solution A; 7.8g cobalt nitrate is dissolved in 35.0mL deionized water, then 5.0g citric acid is joined in above-mentioned cobalt nitrate solution, stirring and dissolving, obtains the solution B containing cobalt.
Take 38.0g attapulgite clay, 146.7g dolomol, 36.4g boehmite, 22.5g metatitanic acid, 3.0g sesbania powder and mix, add solution A, mediate evenly; Add solution B, kneading, moulding, dry naturally, then roasting again, and temperature-rise period adopts the mode of gradient increased temperature, and 20 ℃ are warming up to 200 ℃ through 1h, constant temperature 1h at 200 ℃, then be warming up to 550 ℃ through 1h, roasting 3h, is then cooled to room temperature naturally.
Sulfur-resistant transformation catalyst C-4 gets product.Its intensity, pore structure and pressurization activity data are in table 1,2.
Embodiment 5
First by attapulgite clay at 400 ℃ of roasting temperature 5h, then pulverized 240 mesh sieves, obtain heat treated attapulgite clay.By 9.8g ammonium molybdate 35.0mL deionized water dissolving, obtain the solution A containing molybdenum; By 13.6g cobalt acetate 30.0mL deionized water dissolving; 3.0g oxalic acid is joined in above-mentioned solution, stirring and dissolving, obtains the mixed solution B containing cobalt again.
Take 19.0g attapulgite clay, 15.0g magnesia, 38.5g aluminium oxide, 20.0g metatitanic acid, 3.0g field mountain valley with clumps of trees and bamboo powder and mix, add solution A, mediate evenly; Add solution B, kneading, moulding, dry naturally, then roasting again, and temperature-rise period adopts the mode of gradient increased temperature, and 20 ℃ are warming up to 200 ℃ through 1h, constant temperature 1h at 200 ℃, then be warming up to 500 ℃ through 1h, roasting 4h, is then cooled to room temperature naturally.
Obtain finished product sulfur-resistant transformation catalyst C-5.Its intensity, pore structure and pressurization activity data thereof are in table 1,2.
First by attapulgite clay at 600 ℃ of roasting temperature 6h, then pulverized 240 mesh sieves, obtain heat treated attapulgite clay.By 11.1g ammonium molybdate 40.0mL deionized water dissolving, obtain the solution A containing molybdenum; By 11.6g cobalt acetate 40.0mL deionized water dissolving; 3.0g oxalic acid and 5.0g sucrose are joined in above-mentioned solution, stirring and dissolving, obtains the mixed solution B containing cobalt again.
Take 30.5g attapulgite clay, 12.0g magnesia, 61.0g aluminium glue, 18.8g metatitanic acid, 3.0g field mountain valley with clumps of trees and bamboo powder and mix, add solution A, mediate evenly; Add solution B, kneading, moulding, dry naturally, then roasting again, and temperature-rise period adopts the mode of gradient increased temperature, and 20 ℃ are warming up to 200 ℃ through 1h, constant temperature 1h at 200 ℃, then be warming up to 550 ℃ through 1h, roasting 6h, is then cooled to room temperature naturally.
Obtain finished product sulfur-resistant transformation catalyst C-6.Its intensity, pore structure and pressurization activity data thereof are in table 1,2.
Embodiment 7
First by attapulgite clay at 530 ℃ of roasting temperature 5h, then pulverized 240 mesh sieves, obtain heat treated attapulgite clay.By 10.5g ammonium molybdate 40.0mL deionized water dissolving, obtain the solution A containing molybdenum; By 9.7g cobalt nitrate 40.0mL deionized water dissolving; 7.0g citric acid is joined in above-mentioned solution, stirring and dissolving, obtains the mixed solution B containing cobalt again.
Take 29.0g attapulgite clay, 14.0g magnesia, 44.3g boehmite, 18.8g metatitanic acid, 3.0g field mountain valley with clumps of trees and bamboo powder and mix, add solution A, mediate evenly; Add solution B, kneading, moulding, dry naturally, then roasting again, and temperature-rise period adopts the mode of gradient increased temperature, and 20 ℃ are warming up to 200 ℃ through 1h, constant temperature 1h at 200 ℃, then be warming up to 500 ℃ through 1h, roasting 2h, is then cooled to room temperature naturally.
Obtain finished product sulfur-resistant transformation catalyst C-7.Its intensity, pore structure and pressurization activity data thereof are in table 1,2.
First by attapulgite clay at 500 ℃ of roasting temperature 6h, then pulverized 240 mesh sieves, obtain heat treated attapulgite clay.By 10.5g ammonium molybdate 40.0mL deionized water dissolving, obtain the solution A containing molybdenum; By 13.6g cobalt acetate 40.0mL deionized water dissolving; 3.0g oxalic acid and 5g citric acid are joined in above-mentioned solution, stirring and dissolving, obtains the mixed solution B containing cobalt again.
Take 14.5g attapulgite clay, 15.0g magnesia, 55.0g boehmite, 25.0g metatitanic acid, 3.0g field mountain valley with clumps of trees and bamboo powder and mix, add solution A, mediate evenly; Add solution B, kneading, moulding, dry naturally, then roasting again, and temperature-rise period adopts the mode of gradient increased temperature, and 20 ℃ are warming up to 200 ℃ through 1h, constant temperature 1h at 200 ℃, then be warming up to 550 ℃ through 1h, roasting 4h, is then cooled to room temperature naturally.
Obtain finished product sulfur-resistant transformation catalyst C-8.Its intensity, pore structure and pressurization activity data thereof are in table 1,2.
Embodiment 9
First by attapulgite clay at 450 ℃ of roasting temperature 5h, then pulverized 240 mesh sieves, obtain heat treated attapulgite clay.By 8.6g ammonium molybdate 40.0mL deionized water dissolving, obtain the solution A containing molybdenum; By 9.7g cobalt acetate 40.0mL deionized water dissolving; 8.0g citric acid is joined in above-mentioned solution, stirring and dissolving, obtains the mixed solution B containing cobalt again.
Take 34.0g attapulgite clay, 12.0g magnesia, 43.6g boehmite, 17.5g metatitanic acid, 3.0g field mountain valley with clumps of trees and bamboo powder and mix, add solution A, mediate evenly; Add solution B, kneading, moulding, dry naturally, then roasting again, and temperature-rise period adopts the mode of gradient increased temperature, and 20 ℃ are warming up to 200 ℃ through 1h, constant temperature 1h at 200 ℃, then be warming up to 550 ℃ through 1h, roasting 3h, is then cooled to room temperature naturally.
Obtain finished product sulfur-resistant transformation catalyst C-9.Its intensity, pore structure and pressurization activity data thereof are in table 1,2.
First by attapulgite clay at 400 ℃ of roasting temperature 8h, then pulverized 240 mesh sieves, obtain heat treated attapulgite clay.By 8.0g ammonium molybdate 40.0mL deionized water dissolving, obtain the solution A containing molybdenum; By 11.6g cobalt nitrate 40.0mL deionized water dissolving; 5.0g oxalic acid is joined in above-mentioned solution, stirring and dissolving, obtains the mixed solution B containing cobalt again.
Take 20.0g attapulgite clay, 15.0g magnesia, 55.0g boehmite, 21.3g metatitanic acid, 3.0g field mountain valley with clumps of trees and bamboo powder and mix, add solution A, mediate evenly; Add solution B, kneading, moulding, dry naturally, then roasting again, and temperature-rise period adopts the mode of gradient increased temperature, and 20 ℃ are warming up to 200 ℃ through 1h, constant temperature 1h at 200 ℃, then be warming up to 550 ℃ through 1h, roasting 2h, is then cooled to room temperature naturally.
Obtain finished product sulfur-resistant transformation catalyst C-10.Its intensity, pore structure and pressurization activity data thereof are in table 1,2.
The catalyst of preparing in above-described embodiment 1-10 carries out HTHP hydrothermal treatment consists, and experimental condition is: on former granularity pressurization evaluating apparatus, and take nitrogen and water vapour as medium, dry gas air speed: 4000h
-1; Pressure: 4.0MPa; Evaluate inlet temperature: 350 ℃; Catalyst loading amount: 20.0mL; Liquid to steam ratio is under 1.8 conditions, to process 100 hours.After off-test, take out catalyst and dry, detecting catalyst Strength Changes, the results are shown in Table 1, and the catalyst hydration-resisting performance after hydrothermal treatment consists is good, does not find the phase structure containing hydration peak.
The catalyst pressurization activity rating of preparing in above-described embodiment 1-10, the results are shown in Table 2:
Pressurization activity rating device in known technology and flow process as shown in Figure 1, for simulating under industrial condition, are measured CO concentration and the variation thereof of original catalyst particle size under different condition, the properties such as evaluation of catalyst activity and stability.Adopting the front process gas of certain synthetic ammonia workshop conversion is unstripped gas, allocates appropriate H into
2s, according to the requirement of different WGRs, makes the steam of high-temperature gasification react in reaction tube with unstripped gas, tail gas chromatograph after reaction.
Pressurization appreciation condition is: unstripped gas composition, CO 47～49%(V/V), CO
25～10%(V/V), H
2s>0.05%(V/V), remaining is hydrogen; Dry gas air speed: 3000h
-1; Pressure: 4.0MPa; Evaluate inlet temperature: 250 ℃; Catalyst loading amount: 100mL.
CO interconversion rate computing formula is: X
cO=(Y
cO– Y
cO ')/[Y
cO(1+Y
cO ')] × 100%
Y
cOthe molar fraction (butt) of-Reactor inlet gas CO
Y
cO 'the molar fraction (butt) of-reactor outlet gas CO
Table 1 catalyst pore volume, specific surface and Strength Changes
The pressurization of table 2 catalyst is active
Claims (10)
1. a sulfur-resistant transformation catalyst, is characterized in that: its chemical composition is by percentage to the quality:
Cobalt compound, in CoO, content is 1.0～4.5%;
Molybdate compound, with MoO
3meter, content is 5.0～10.0%;
Magnesium-containing compound, in MgO, content is 10.0～17.0%;
Aluminum contained compound, with Al
2o
3meter, content is 30.0～43.5%;
Titanium-containing compound, with TiO
2meter, content is 14.5～20.0%;
Surplus is the attapulgite clay of heat treatment modification.
2. a preparation method for sulfur-resistant transformation catalyst claimed in claim 1, is characterized in that comprising the steps:
1. prepare heat treatment modified attapulgite clay:
Adopt the mode of roasting to prepare heat treatment modified attapulgite clay, sintering temperature is 400～600 ℃, roasting time is 2～8h, then carry out the above granularity content of pulverization process to 240 order and be not less than 90%, obtain heat treatment modified attapulgite clay, contained magnesia, silica and aluminium oxide total content are higher than 75%;
2. the preparation of active component solution:
By molybdate compound deionized water dissolving, obtain solution A; By cobalt compound deionized water dissolving, then binding agent is added wherein, stirring and dissolving, obtains solution B;
3. shaping of catalyst:
The attapulgite clay of heat treatment modification with powdered compounds containing the powdered compounds of magnesium, titaniferous, mix containing powdered compounds and the pore creating material of aluminium, is added to solution A, mediate evenly; Add again solution B, mediate evenly extruded moulding;
4. dry:
Catalyst after moulding is at room temperature placed 24～48h and is naturally dried;
5. roasting:
Dried catalyst carries out calcination process, and temperature-rise period adopts the mode of gradient increased temperature, and 20 ℃ are warming up to 200 ℃ through 1h, constant temperature 1h at 200 ℃, then be warming up to required sintering temperature through 1h, and sintering temperature is 400～600 ℃, roasting time is 2～8h.
3. the preparation method of sulfur-resistant transformation catalyst according to claim 2, is characterized in that: described cobalt compound is selected from cobalt nitrate or cobalt acetate.
4. the preparation method of sulfur-resistant transformation catalyst according to claim 2, is characterized in that: described molybdate compound is selected from ammonium molybdate.
5. the preparation method of sulfur-resistant transformation catalyst according to claim 2, is characterized in that: the described powdered compounds containing magnesium is selected from magnesia, magnesium oxalate, magnesium carbonate or dolomol.
6. the preparation method of sulfur-resistant transformation catalyst according to claim 2, is characterized in that: the described powdered compounds containing aluminium is selected from boehmite, aluminium glue or aluminium oxide.
7. the preparation method of sulfur-resistant transformation catalyst according to claim 2, is characterized in that: the powdered compounds of described titaniferous is selected from metatitanic acid, titanium oxide or anatase.
8. the preparation method of sulfur-resistant transformation catalyst according to claim 2, is characterized in that: described binding agent is selected from one or more in water, acetic acid, citric acid, oxalic acid or nitric acid.
9. the preparation method of sulfur-resistant transformation catalyst according to claim 2, is characterized in that: described pore creating material is selected from polyvinyl alcohol, poly amic acid, field mountain valley with clumps of trees and bamboo powder, citric acid, starch or sucrose.
10. according to the preparation method of the arbitrary described sulfur-resistant transformation catalyst of claim 2-9, it is characterized in that: the specific surface of the sulfur-resistant transformation catalyst making is 100～160m
2g
-1, pore volume 0.2～0.5cm
3g
-1.
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