CN103769116B - Sulfur-resistant transformation catalyst and preparation method - Google Patents

Sulfur-resistant transformation catalyst and preparation method Download PDF

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CN103769116B
CN103769116B CN201210402772.9A CN201210402772A CN103769116B CN 103769116 B CN103769116 B CN 103769116B CN 201210402772 A CN201210402772 A CN 201210402772A CN 103769116 B CN103769116 B CN 103769116B
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sulfur
preparation
transformation catalyst
resistant transformation
attapulgite clay
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CN103769116A (en
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赵庆鲁
余汉涛
白志敏
齐焕东
田兆明
王昊
姜建波
薛红霞
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China Petroleum and Chemical Corp
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The present invention relates to a kind of sulfur-resistant transformation catalyst and preparation method.Described sulfur-resistant transformation catalyst is with Co, Mo for active component, and not containing potassium and rare earth compound, carrier adopts the attapulgite clay Some substitute tradition magnalium material of heat treatment modification.In preparation process, adopt heat treatment to replace acid treatment mode to natural attapulgite clay, avoid the process to acid pickle; Prepared by employing kneading method, active component is uniformly dispersed, and not easily runs off, and adds the activity stability of catalyst, and compared with the infusion process of prior art, both saved preparation water consumption, in turn simplify preparation process and operational sequence, cost advantage is obvious.This catalyst 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, conversion section in New Coal Chemical can be met and, to the requirement of transformation catalyst, there is good application value.

Description

Sulfur-resistant transformation catalyst and preparation method
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 the 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, resistant to sulfur 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 obtain, and its active component is generally selected from cobalt and molybdenum be representative VIII race and group vib metallic compound, 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 containing elements such as Mg, Al, Ti.
Natural attapulgite clay, also known as palygorskite, is take attapulgite as a kind of clay mineral of 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 more than 70% of global reserves, but its utilization is still more in the extensive style exploitation process segment.Mainly for the production of the primary product that the technology contents such as exterior coating, compound fertilizer binding agent and feed addictive are lower, product lacks scientific and technological content, and added value is on the low side, and price is comparatively cheap.Along with deepening continuously of developing attapulgite clay, carrier material cheap and easy to get is it can be used as to show 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.Adopt the method for dipping-precipitation by the oxide of nanoscale or its salt dopping in acid-treated attapulgite clay, preparation respective carrier, flood cobalt active component of cobalt afterwards and prepare cobalt molybdenum system CO sulfur-resistant transformation catalyst.Recessed native carrier is relative to commercial active carbon, γ-Al 2o 3, MgAl 2o 4cheap in carrier, have larger commercial Application meaning, but method water consumption described in this invention is large, containing sour water difficult treatment, preparation section is complicated.
Summary of the invention
The object of the invention is to provide a kind of sulfur-resistant transformation catalyst and preparation method, as the carrier component of catalyst after the heat treatment of this catalyst employing attapulgite clay, reduces preparation cost, avoids the process to acid pickle; Have that intensity is high, pore volume and specific surface is suitable, hydration-resisting performance and having good stability, to meet in New Coal Chemical conversion section to the requirement of transformation catalyst.
Sulfur-resistant transformation catalyst of the present invention, comprise carrier and active component, its be using the modified attapulgite clay of heat treatment 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 total content of alumina 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, shaping, dry, roasting, and obtained finished catalyst, comprises the steps:
1. heat treatment modified attapulgite clay is prepared:
The mode of roasting is adopted to prepare heat treatment modified attapulgite clay, sintering temperature is 400 ~ 600 DEG C, roasting time is 2 ~ 8h, then carry out the above granularity content of pulverization process to 240 order and be not less than 90%, namely obtain heat treatment modified attapulgite clay, contained magnesia, silica and total content of alumina 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 add wherein by binding agent, stirring and dissolving, obtains solution B;
3. shaping of catalyst:
The attapulgite clay of heat treatment modification is mixed with the powdered compounds containing the powdered compounds of magnesium, titaniferous, the powdered compounds containing aluminium and pore creating material, adds solution A, mediate evenly; Add solution B again, mediate evenly, extruded moulding;
4. dry:
Catalyst after shaping 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 DEG C are warming up to 200 DEG C through 1h, constant temperature 1h at 200 DEG C, then are warming up to required sintering temperature through 1h, and sintering temperature is 400 ~ 600 DEG C, and roasting time is 2 ~ 8h.
Described cobalt compound is selected from cobalt nitrate or cobalt acetate, preferred 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, preferred boehmite.
The powdered compounds of described titaniferous is selected from metatitanic acid, titanium oxide or anatase, preferred 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, preferred sesbania powder, and the addition in preparation process is 1 ~ 8% of finished catalyst quality, and preferably 2 ~ 4%;
Described binding agent be selected from water, acetic acid, citric acid, oxalic acid or nitric acid one or more, optimization citric acid and/or oxalic acid, the addition in preparation process is 1 ~ 8% of finished catalyst quality, preferably 2 ~ 4%.Binding agent and bulk catalyst component compatibility well, 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, conversion section can be met in New Coal Chemical to the requirement of transformation catalyst.
This catalyst adopts wide material sources, attapulgite clay Some substitute magnalium material with low cost, reduces catalyst preparing cost; This catalyst adopts heat treatment mode to replace acid treatment mode to natural attapulgite clay, avoids the process to acid pickle; This catalyst adopts kneading method preparation, active component is uniformly dispersed in the carrier, not easily run off, add the activity stability of catalyst, compared with the infusion process of prior art, both save preparation water consumption, in turn simplify preparation process and operational sequence, cost advantage is remarkable, has good economic benefit and popularizing application prospect.
Accompanying drawing explanation
Fig. 1 is that the present invention pressurizes activity rating apparatus structure schematic diagram;
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.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described further.
Embodiment 1
First by attapulgite clay roasting 3h at 600 DEG C, then pulverized 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, obtain 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 mix, add solution A, mediate evenly; Add solution B again, mediate, shaping, naturally dry, then roasting, the mode of temperature-rise period employing gradient increased temperature, 20 DEG C are warming up to 200 DEG C through 1h, constant temperature 1h at 200 DEG C, then are warming up to 500 DEG C through 1h, and 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.
Embodiment 2
First by attapulgite clay at 580 DEG C of roasting temperature 3h, then pulverized 240 mesh sieves, obtained 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, obtain 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 mix, add solution A, mediate evenly; Add solution B again, mediate, shaping, naturally dry, then roasting, the mode of temperature-rise period employing gradient increased temperature, 20 DEG C are warming up to 200 DEG C through 1h, constant temperature 1h at 200 DEG C, then are warming up to 530 DEG C through 1h, and roasting 3h, is down to room temperature naturally.
Namely sulfur-resistant transformation catalyst C-2 is obtained.Its intensity, pore structure and pressurization activity data thereof are in table 1,2.
Embodiment 3
First by attapulgite clay at 550 DEG C of roasting temperature 3h, then pulverized 240 mesh sieves, obtained 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, obtain 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 mix, add solution A, mediate evenly; Add solution B again, mediate, shaping, naturally dry, then roasting, the mode of temperature-rise period employing gradient increased temperature, 20 DEG C are warming up to 200 DEG C through 1h, constant temperature 1h at 200 DEG C, then are warming up to 550 DEG C through 1h, and roasting 2h, then Temperature fall is to room temperature.
Namely finished product sulfur-resistant transformation catalyst C-3 is obtained.Its intensity, pore structure and pressurization activity data thereof are in table 1,2.
Embodiment 4
First by attapulgite clay at 500 DEG C of roasting temperature 3h, then pulverized 240 mesh sieves, obtained 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, obtain the solution B containing cobalt.
Take 38.0g attapulgite clay, 146.7g dolomol, 36.4g boehmite, 22.5g metatitanic acid, 3.0g sesbania powder mix, add solution A, mediate evenly; Add solution B again, mediate, shaping, naturally dry, then roasting, the mode of temperature-rise period employing gradient increased temperature, 20 DEG C are warming up to 200 DEG C through 1h, constant temperature 1h at 200 DEG C, then are warming up to 550 DEG C through 1h, and roasting 3h, then Temperature fall is to room temperature.
Get product sulfur-resistant transformation catalyst C-4.Its intensity, pore structure and pressurization activity data are in table 1,2.
Embodiment 5
First by attapulgite clay at 400 DEG C of roasting temperature 5h, then pulverized 240 mesh sieves, obtained 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; Again 3.0g oxalic acid is joined in above-mentioned solution, stirring and dissolving, obtain the mixed solution B containing cobalt.
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 mix, add solution A, mediate evenly; Add solution B again, mediate, shaping, naturally dry, then roasting, the mode of temperature-rise period employing gradient increased temperature, 20 DEG C are warming up to 200 DEG C through 1h, constant temperature 1h at 200 DEG C, then are warming up to 500 DEG C through 1h, and roasting 4h, then Temperature fall is to room temperature.
Namely finished product sulfur-resistant transformation catalyst C-5 is obtained.Its intensity, pore structure and pressurization activity data thereof are in table 1,2.
Embodiment 6
First by attapulgite clay at 600 DEG C of roasting temperature 6h, then pulverized 240 mesh sieves, obtained 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; Again 3.0g oxalic acid and 5.0g sucrose are joined in above-mentioned solution, stirring and dissolving, obtain the mixed solution B containing cobalt.
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 mix, add solution A, mediate evenly; Add solution B again, mediate, shaping, naturally dry, then roasting, the mode of temperature-rise period employing gradient increased temperature, 20 DEG C are warming up to 200 DEG C through 1h, constant temperature 1h at 200 DEG C, then are warming up to 550 DEG C through 1h, and roasting 6h, then Temperature fall is to room temperature.
Namely finished product sulfur-resistant transformation catalyst C-6 is obtained.Its intensity, pore structure and pressurization activity data thereof are in table 1,2.
Embodiment 7
First by attapulgite clay at 530 DEG C of roasting temperature 5h, then pulverized 240 mesh sieves, obtained 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; Again 7.0g citric acid is joined in above-mentioned solution, stirring and dissolving, obtain the mixed solution B containing cobalt.
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 mix, add solution A, mediate evenly; Add solution B again, mediate, shaping, naturally dry, then roasting, the mode of temperature-rise period employing gradient increased temperature, 20 DEG C are warming up to 200 DEG C through 1h, constant temperature 1h at 200 DEG C, then are warming up to 500 DEG C through 1h, and roasting 2h, then Temperature fall is to room temperature.
Namely finished product sulfur-resistant transformation catalyst C-7 is obtained.Its intensity, pore structure and pressurization activity data thereof are in table 1,2.
Embodiment 8
First by attapulgite clay at 500 DEG C of roasting temperature 6h, then pulverized 240 mesh sieves, obtained 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; Again 3.0g oxalic acid and 5g citric acid are joined in above-mentioned solution, stirring and dissolving, obtain the mixed solution B containing cobalt.
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 mix, add solution A, mediate evenly; Add solution B again, mediate, shaping, naturally dry, then roasting, the mode of temperature-rise period employing gradient increased temperature, 20 DEG C are warming up to 200 DEG C through 1h, constant temperature 1h at 200 DEG C, then are warming up to 550 DEG C through 1h, and roasting 4h, then Temperature fall is to room temperature.
Namely finished product sulfur-resistant transformation catalyst C-8 is obtained.Its intensity, pore structure and pressurization activity data thereof are in table 1,2.
Embodiment 9
First by attapulgite clay at 450 DEG C of roasting temperature 5h, then pulverized 240 mesh sieves, obtained 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; Again 8.0g citric acid is joined in above-mentioned solution, stirring and dissolving, obtain the mixed solution B containing cobalt.
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 mix, add solution A, mediate evenly; Add solution B again, mediate, shaping, naturally dry, then roasting, the mode of temperature-rise period employing gradient increased temperature, 20 DEG C are warming up to 200 DEG C through 1h, constant temperature 1h at 200 DEG C, then are warming up to 550 DEG C through 1h, and roasting 3h, then Temperature fall is to room temperature.
Namely finished product sulfur-resistant transformation catalyst C-9 is obtained.Its intensity, pore structure and pressurization activity data thereof are in table 1,2.
Embodiment 10
First by attapulgite clay at 400 DEG C of roasting temperature 8h, then pulverized 240 mesh sieves, obtained 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; Again 5.0g oxalic acid is joined in above-mentioned solution, stirring and dissolving, obtain the mixed solution B containing cobalt.
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 mix, add solution A, mediate evenly; Add solution B again, mediate, shaping, naturally dry, then roasting, the mode of temperature-rise period employing gradient increased temperature, 20 DEG C are warming up to 200 DEG C through 1h, constant temperature 1h at 200 DEG C, then are warming up to 550 DEG C through 1h, and roasting 2h, then Temperature fall is to room temperature.
Namely finished product sulfur-resistant transformation catalyst C-10 is obtained.Its intensity, pore structure and pressurization activity data thereof are in table 1,2.
The catalyst prepared in above-described embodiment 1-10 carries out HTHP hydrothermal treatment consists, and experimental condition is: on former granularity pressurization evaluating apparatus, with nitrogen and water vapour for medium, and dry gas air speed: 4000h -1; Pressure: 4.0MPa; Evaluate inlet temperature: 350 DEG C; Catalyst loading amount: 20.0mL; Liquid to steam ratio is process 100 hours under 1.8 conditions.Take out catalyst after off-test to dry, detecting catalyst Strength Changes, the results are shown in Table 1, and the catalyst hydration-resisting after hydrothermal treatment consists is functional, does not find the phase structure containing hydration peak.
The catalyst pressurization activity rating prepared 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, under simulating industrial condition, measure original catalyst particle size CO concentration at different conditions and change thereof, the properties such as evaluation of catalyst activity and stability.Before adopting certain synthetic ammonia workshop to convert, process gas is unstripped gas, allocates appropriate H into 2s, according to the requirement of different WGR, makes the steam of high-temperature gasification and unstripped gas react in reaction tube, tail gas chromatograph after reaction.
Pressurization appreciation condition is: unstripped gas forms, CO47 ~ 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 DEG C; 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 according to claim 1, is characterized in that comprising the steps:
1. heat treatment modified attapulgite clay is prepared:
The mode of roasting is adopted to prepare heat treatment modified attapulgite clay, sintering temperature is 400 ~ 600 DEG C, roasting time is 2 ~ 8h, then carry out the above granularity content of pulverization process to 240 order and be not less than 90%, namely obtain heat treatment modified attapulgite clay, contained magnesia, silica and total content of alumina 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 add wherein by binding agent, stirring and dissolving, obtains solution B;
3. shaping of catalyst:
The attapulgite clay of heat treatment modification is mixed with the powdered compounds containing the powdered compounds of magnesium, titaniferous, the powdered compounds containing aluminium and pore creating material, adds solution A, mediate evenly; Add solution B again, mediate evenly, extruded moulding;
4. dry:
Catalyst after shaping 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 DEG C are warming up to 200 DEG C through 1h, constant temperature 1h at 200 DEG C, then are warming up to required sintering temperature through 1h, and sintering temperature is 400 ~ 600 DEG C, and 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 be selected from water, acetic acid, citric acid, oxalic acid or nitric acid one or more.
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 obtained sulfur-resistant transformation catalyst is 100 ~ 160m 2g -1, pore volume 0.2 ~ 0.5cm 3g -1.
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