CN1836768A - Claus tail gas hydrogenation catalyst - Google Patents
Claus tail gas hydrogenation catalyst Download PDFInfo
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Abstract
The Claus tail gas hydrogenating catalyst is prepared with aluminum hydroxide powder and aluminum hydroxide gum modified with great pore volume and great specific surface area silicon as main materials and through rolling to from ball, curing, stoving and roasting to prepare carrier, and soaking in solution containing VIB and VIII metal salt. The prepared catalyst is spherical, and has specific surface area greater than 260 sq m/g, pore volume greater than 0.35 ml/g, high side pressure strength, homogeneously dispersed active component, high organic sulfide hydrogenolyzing activity, high CS2 and COS hydrolysis activity and high activity stability. It is used in Claus tail gas hydrogenating process.
Description
Technical field
The present invention relates to a kind of Claus (Crouse) tail-gas hydro-conversion catalyst.
Background technology
In sulphur recovery Claus tail gas reduction absorption technique, sour gas is after secondary Crouse transforms, enter hydrogenation reactor, under the effect of hydrogenation catalyst, elemental sulfur in the tail gas, sulfur-containing compound hydrogenation or hydrolysis are converted into hydrogen sulfide, adopt amine liquid to select to absorb then, the tail gas after the purification enters atmosphere.One of this technology key technology is supporting high activity sulfur-containing compound (or elemental sulfur) hydrogenation conversion catalyst.
At present the hydrogenation on tail gas of sulphur patent of foreign application adopts two-stage process more, i.e. the hydrogenation reactor top hydrolyst of packing into, the bottom hydrogenation catalyst of packing into.As 1994 Japan Patent on May 10, (patent No. JP06127907A2) a kind of sulfur-bearing Claus tail gas hydrogenation treatment process and catalyst are disclosed, adopt two kinds of catalyst to pack in the same reactor in this patent, top is the MoO3/TiO2 catalyst, and wherein MoO3 content reaches 16%; The bottom is the Co-Mo/AL203 catalyst, and wherein MoO3 content reaches 13%, and CoO is 3.5%.International Shell Co. Ltd is at Chinese patents CN1230134, this patent disclosure a kind of catalyzer for hydrogenation on tail gas of sulphur, this catalyst is a carrier with silica and aluminium oxide, wherein silica content is greater than 25%, with nickel, molybdenum is active component, needs to use with being loaded in the reactor with COS, CS2 hydrolytic reagent (K/TiO2).
The commercial plant of the hydrogenation on tail gas of sulphur technology of domestic-developed and existing operation all adopts single device list agent technology.Used catalyzer for hydrogenation on tail gas of sulphur has the CT6-5 of natural gas research institute of Southwest Oil branch company of PetroChina Company Limited. exploitation and the LS-951CoMo/Al2O3 catalyst of CT6-5BCoMo/Al2O3 catalyst and the exploitation of Shandong research institute of branch company of China Petrochemical Industry.As " oil and gas chemical industry " 04 phase in 1998, Xiao Jintang has reported " CT6-5 reduction absorption process is handled the sulphur recovery catalyzer for hydrogenation on tail gas ", and this catalyst is carrier with the ball-aluminium oxide, and the dipping active constituent is prepared from, specific area is 196m2/g, and pore volume is 0.192ml/g." oil and gas chemical industry " 05 phase in 2002, Geng Yanqing has reported " realizing the tail gas qualified discharge with CT6-5B catalyst treatment Claus tail gas ", and the CT6-5B catalyst is with sphere, and specific area is 199m2/g, and pore volume is 0.251ml/g.Not seeing above-mentioned two kinds of catalyst applies for a patent.
The preparation method of a kind of catalyzer for hydrogenation on tail gas of sulphur of the open Shandong branch company of China Petrochemical Industry of Chinese patent (02135699.8), Preparation of Catalyst comprises aluminum hydroxide solid elastomer kneading, extrusion, oven dry, roasting is prepared into alumina support, then with the solution impregnating carrier that contains cobalt molybdenum salt, process such as drying, roasting is prepared into catalyst again.Because the hydrogenation on tail gas of sulphur device generally adopts horizontal reactor, adopt bar shaped (or clover) catalyst loading and unloading of this patent preparation not have ball shape catalyst convenient, particularly when unloading catalyst, be difficult for separating, prolong the catalyst loading and unloading time with the porcelain ball of reaction bed upper and lower part.The specific area of this catalyst is still waiting to improve.
Summary of the invention
Technical problem to be solved by this invention provides a kind of Claus tail-gas hydrogenation catalyst, under the situation that guarantees the easy roller forming of catalyst, make catalyst have higher side pressure strength, bigger pore volume, specific area, and also catalyst not only has hydrogenation activity and also has hydrolysis COS, CS
2Activity.
Claus tail-gas hydrogenation catalyst of the present invention, comprise alumina support and group vib or VIII family metal oxide active component, it is characterized in that described alumina support is to be made by the aluminum hydroxide solid elastomer of fast shedding of aluminium hydroxide and silicon modification, the mass ratio of the aluminum hydroxide solid elastomer of fast shedding of aluminium hydroxide and silicon modification is 1: 0.1-2, preferred 1: 0.2-0.5, aluminum hydroxide solid elastomer is with Al
2O
3The quality meter, modifier is with SiO
2The quality meter, modifier SiO
2Amount be Al in the aluminum hydroxide solid elastomer
2O
3The 1-10% of amount, preferred 2-5%.
It is pore volume greater than 0.8 milliliter/gram that the present invention prepares the used aluminum hydroxide solid elastomer of carrier, and specific surface is greater than 350 meters squared per gram, and preferably pore volume is greater than 1.0 milliliters/gram, and specific surface is greater than 400 meters squared per gram.The fast shedding of used aluminium hydroxide is a pore volume greater than 0.3 milliliter/gram, and specific surface is greater than 260 meters squared per gram, and preferably pore volume is greater than 0.4 milliliter/gram, and specific surface is greater than 300 meters squared per gram.
The present invention utilizes silica modified, and modifier is the inorganic salts of silicon, as sodium metasilicate.Adopt the aluminum hydroxide solid elastomer of silicon modification, make catalyst have COS, CS preferably simultaneously
2Hydrolysing activity, SiO simultaneously
2Content is moderate, the hydrolysing activity height of COS, CS2.
The preparation of carrier is according to common Preparation of catalysts method, by raw material mix with binding agent, moulding, slaking, oven dry, roasting form, used binding agent all is the common selection component of catalyst, can be water, nitric acid, acetic acid, Ludox, aluminium colloidal sol, be preferably water or nitric acid, addition is the 2-10% (m/m) of aluminium hydroxide gross weight (the weight summation of fast shedding of aluminium hydroxide and silicone modified aluminum hydroxide solid elastomer), is preferably 4-6% (m/m).
Silicone modified aluminum hydroxide solid elastomer should carry out fast dewatering before using, and dehydration temperaturre 480-600 ℃, time 0.5-2 hour.
Carrier slaking atmosphere is steam, curing temperature 50-100 ℃, and time 5-12 hour.
The carrier bake out temperature is 60-150 ℃, and be 2-20 hour drying time, is preferably 110-120 ℃, dry 2-4 hour.Sintering temperature is 380-500 ℃, roasting time 2-8 hour, is preferably 420-480 ℃, roasting 4 hours.
Still be common group vib and VIII family metallic element as the hydrogenation activity component that catalyzer for hydrogenation on tail gas of sulphur of the present invention adopted, it is made into uniform and stable solution, impregnated carrier is prepared from.The group vib metal generally is selected from molybdenum, tungsten, molybdenum preferably, and its predecessor can adopt ammonium molybdate, and the group vib metal oxide accounts for the 5-15% (m/m) of catalyst total amount, preferred 8～11%; VIII family metal generally is selected from cobalt, nickel, cobalt preferably, and its predecessor can adopt cobalt nitrate or cobalt acetate, and the VIII family metal oxide accounts for the 0.5-5% (m/m) of catalyst total amount, preferred 1～3%.
The prepared sulphur Claus tail-gas hydrogenation catalyst outward appearance of the present invention is spherical in shape.
Preparation of catalysts method of the present invention comprises:
1. choose pore volume and be 0.9～1.2 milliliter/gram, specific area was the silicone modified aluminum hydroxide solid elastomer of 350～500 meters squared per gram, 480-600 ℃ of fast dewatering 0.5～2 hour.
2. choose pore volume greater than 0.4 milliliter/gram, specific area is greater than the fast shedding of the aluminium hydroxide of 300 meters squared per gram, by a certain percentage with above-mentioned fast dewatering after dry glue powder mix, the material that mixes is labeled as material 1.
3. take by weighing in a certain proportion of binding agent (as nitric acid, acetic acid, aluminium colloidal sol, Ludox) one or more, be mixed with certain density solution 1.
4. material 1 part is placed in the bowling machine, rotate bowling machine, in bowling machine, spray the solution 1 for preparing, form small spheric granules gradually, the limit adds material 1 then, limit spray solution 1, treat that most of balling-up granularity takes out behind 3～5mm, sieve, sift out the bead of 3～5mm.
5. above-mentioned bead is placed the atmosphere of 100% steam, hydration slaking 5～12 hours.
6. 80～150 ℃ of oven dry of the bead after the slaking are 2～20 hours, in 380～500 ℃ of roastings 2～6 hours, can make large pore volume (greater than 0.45 milliliter/gram), the spherical Al of bigger serface (greater than 320 meters squared per gram)
20
3Carrier.
7. get the ammoniacal liquor of a certain amount of concentration 22～28%, the cobalt salt that adds aequum, as cobalt nitrate or cobalt acetate, under constantly stirring, add a certain amount of ethylenediamine of people, make it to form stable cobalt ethylenediamine complex compound, the amount that makes ethylenediamine is that 1/50～1/7 of cobalt nitrate weight is preferably 1/20～1/15, adds the ammonium molybdate of aequum then, is stirred to dissolving fully.
8. get a certain amount of above-mentioned co-impregnated solution, according to equi-volume impregnating impregnated carrier 1～2 hour, in 50～60 ℃ of oven dry 2-4 hour, 110～120 ℃ of oven dry 2-4 hour in 400～500 ℃ of roastings 3～4 hours, made the Claus catalyzer for hydrogenation on tail gas.Cobalt oxide content is 0.5～5% (m/m) in the catalyst of the present invention's preparation, preferably 1～3.0 (m/m); Molybdenum oxide content 5～15.0 (m/m), 8～11% (m/m) preferably, all the other are AL
2O
3
Advantage of the present invention:
Catalyst pore volume, specific area are bigger, and pore volume is greater than 0.35 milliliter/gram, and specific area is greater than 260 meters squared per gram, and active component high degree of dispersion modifier content is moderate, COS, CS
2The hydrolysing activity height, the sulfur-containing compound hydrogenolysis is active high, the side pressure strength height, wear away low, water-fast Heat stability is good, anti-efflorescence ability is strong.The easy balling-up of catalyst, easy to loading and unloading.
The specific embodiment
In following examples in the silicone modified aluminum hydroxide solid elastomer powder content of silica be that aluminum hydroxide solid elastomer is with Al
2O
3The quality meter, SiO
2Amount account for Al in the aluminum hydroxide solid elastomer
2O
3The mass percent of amount.
Embodiment 1
Taking by weighing the 10Kg pore volume is 1.2 milliliters/gram, and specific area is that 438 meters squared per gram, dioxide-containing silica are 2.5% silicone modified aluminum hydroxide solid elastomer powder, places 600 ℃ of roasters, and fast dewatering 1 hour obtains material 1.Taking by weighing pore volume is 0.43 milliliter/gram, and specific area is the fast shedding 40Kg of the aluminium hydroxide of 321 meters squared per gram, mixes with material 1.
Configuration concentration is the nitric acid of 8% (m/m), and adding 4kg concentration is 25% Ludox, is made into uniform solution.The above-mentioned material that mixes is placed bowling machine, the solution that configures is slowly sprayed in the above-mentioned material that mixes, rotate roller forming, sieve, sift out the bead of 3～5mm, place the atmosphere of 100% steam, hydration maintenance 10 hours is in 120 ℃ of oven dry 6 hours, in 450 ℃ of roastings 4 hours, making pore volume is 0.49 milliliter/gram, and specific area is the spherical Al of 330 meters squared per gram
2O
3Carrier.
Get 70ml concentration and be 22～28% ammoniacal liquor, be heated to 70 ℃, add 18 gram cobalt nitrates, under constantly stirring, add people 1ml ethylenediamine, make it to form stable cobalt ethylenediamine complex compound, add the ammonium molybdate of aequum then, be stirred to dissolving fully, ammoniacal liquor is settled to 100ml.
Get the above-mentioned co-impregnated solution of 50ml, flooded the 100g carrier 1～2 hour, in 50～60 ℃ of oven dry 2-4 hour according to equi-volume impregnating, dried 2-4 hour for 110～120 ℃, in 400～500 ℃ of roastings 3～4 hours, make Claus catalyzer for hydrogenation on tail gas A, its physico-chemical property sees Table 1.
Comparative Examples 1 (mass ratio of fast shedding of this Comparative Examples aluminium hydroxide and silicone modified aluminum hydroxide solid elastomer powder is 1: 4)
The preparation method is with embodiment 1, and taking by weighing the 40Kg pore volume is 1.2 milliliters/gram, and specific area is the silicone modified aluminum hydroxide solid elastomer powder of 438 meters squared per gram, places 600 ℃ of roasters, and fast dewatering 1 hour obtains material 1.Take by weighing that pore volume is 0.43 a milliliter/gram after the hydration, specific area is the fast shedding 10Kg of the aluminium hydroxide of 321 meters squared per gram, mixes the ball type carrier of preparation with material 1.The dipping active constituent makes catalyst B, and its physico-chemical property sees Table 1.
Comparative Examples 2
The preparation method does not add the fast shedding of aluminium hydroxide with embodiment 1 in the preparation process, all use aluminum hydroxide solid elastomer, the ball type carrier of preparation.The dipping active constituent makes catalyst D, and its physico-chemical property sees Table 1.
Comparative Examples 3
The preparation method does not add the aluminum hydroxide solid elastomer powder with embodiment 1 in the preparation process, all use the fast shedding of aluminium hydroxide, the ball type carrier of preparation, and the dipping active constituent makes catalyst E, and its physico-chemical property sees Table 1.
Comparative Examples 4
The preparation method is with embodiment 1, and taking by weighing the 10Kg pore volume is 0.8 milliliter/gram, and specific area is the pure cerium hydroxide aluminium dry glue powder of 378 meters squared per gram, places 600 ℃ of roasters, and fast dewatering 1 hour obtains material 1.Take by weighing that pore volume is 0.43 a milliliter/gram after the hydration, specific area is the fast shedding 40Kg of the aluminium hydroxide of 321 meters squared per gram, mixes with material 1.The ball type carrier of preparation, the dipping active constituent makes catalyst F, and its physico-chemical property sees Table 1.
The comparison of table 1 catalyst physico-chemical property
| Project | A | B | D | E | F |
| Outward appearance | Spherical | Spherical | Spherical | Spherical | Spherical |
| Size, mm | Φ3-5 | Φ3-5 | Φ3-5 | Φ3-5 | Φ3-5 |
| Cobalt oxide, % | 1.80 | 1.82 | 1.83 | 1.82 | 1.82 |
| Molybdenum trioxide, % | 9.3 | 9.3 | 9.5 | 9.5 | 9.4 |
| Pore volume, ml/g | 0.43 | 0.50 | 0.52 | 0.30 | 0.36 |
| Specific area, m 2/g | 307 | 334 | 352 | 228 | 262 |
| Intensity, N/ | 161 | 68 | 48 | 168 | 162 |
| The heap ratio, kg/l | 0.79 | 0.61 | 0.58 | 0.84 | 0.82 |
Catalyst Claus tail gas hydrogenation activity of conversion is estimated:
Because catalyst B, D intensity difference are difficult to satisfy the commercial plant requirement.Get each 800.0 milliliters of A, E, three kinds of catalyst of F, be loaded in the industrial side line reactor, adopt conventional unstripped gas presulfurization (reactor outlet H
2S content is more than or equal to inlet, and sulfuration finishes), conditions of vulcanization is: 300 ℃ of temperature, volume space velocity 600h
-1, hydrogen content is 0.5-5% (v/v) in the unstripped gas.
Sulfuration switches to Claus tail gas after finishing.At 260 ℃ of reaction temperatures, volume space velocity 2000h
-1, hydrogen content is under the reaction condition greater than 1% (v/v) in the hydrogenation tail gas, assaying reaction device gateway H
2S, COS, SO
2, CO
2Content is table 2.
Several catalyst activities of table 2 relatively
| Catalyst | Reactor inlet gas composition, (v/v) % | Reactor outlet gas is formed, (v/v) % | ||||||||
| H 2S | COS | SO 2 | CO 2 | H 2 | H 2S | COS | SO 2 | CO 2 | H 2 | |
| A E F | 0.48 0.36 0.44 | 0.06 0.04 0.06 | 0.34 0.28 0.18 | 2.02 3.20 4.98 | 3.02 4.12 4.80 | 1.56 1.39 1.28 | - - - | - - - | 2.28 3.56 5.24 | 1.32 2.58 3.46 |
As can be seen from Table 2, under above-mentioned reaction condition, several activity of such catalysts all can satisfy the commercial plant requirement.
Catalyst desulfurizing activity and contrast test:
Get above-mentioned A, E, three kinds of catalyst of F on industrial side line device, after the method sulfuration in, temperature is transferred to 300 ℃, volume space velocity 4000h according to the method described above
-1, hydrogen content is under the reaction condition greater than 1% (v/v) in the hydrogenation tail gas, assaying reaction device gateway H
2S, COS, SO
2, CO
2Content sees Table 3.
Several catalyst high-speed of table 3 specific activity
| Catalyst | Reactor inlet gas composition, (v/v) % | Reactor outlet gas is formed, (v/v) % | ||||||||
| H 2S | COS | SO 2 | CO 2 | H 2 | H 2S | COS | SO 2 | CO 2 | H 2 | |
| A E F | 0.68 0.50 0.56 | 0.02 0.04 0.06 | 0.52 0.32 0.48 | 6.26 4.98 8.24 | 1.80 2.44 2.22 | 2.01 1.79 1.84 | - - - | - 0.06 0.04 | 6.60 5.46 8.96 | 0.56 1.14 1.10 |
As can be seen from Table 3, E, F catalyst can not satisfy the requirement of big air speed reaction.
Embodiment 2:
The preparation method is with embodiment 1, and dioxide-containing silica is 2% in the silicone modified aluminum hydroxide solid elastomer powder, and pore volume is 1.1 a milliliters/gram, and specific area is 418 meters squared per gram.Make catalyst G, its physico-chemical property sees Table 4.
Embodiment 3:
The preparation method is with embodiment 1, and dioxide-containing silica is 1% in the silicone modified aluminum hydroxide solid elastomer powder, and pore volume is 0.94 a milliliter/gram, and specific area is 387 meters squared per gram.Make catalyst H, its physico-chemical property sees Table 4.
Embodiment 4:
The preparation method is with embodiment 1, and dioxide-containing silica is 5% in the silicone modified aluminum hydroxide solid elastomer powder, and pore volume is 1.28 a milliliters/gram, and specific area is 448 meters squared per gram.Make catalyst I, its physico-chemical property sees Table 4.
Embodiment 5:
The preparation method is with embodiment 1, and dioxide-containing silica is 10% in the silicone modified aluminum hydroxide solid elastomer powder, and pore volume is 1.36 a milliliters/gram, and specific area is 457 meters squared per gram.Make catalyst J, its physico-chemical property sees Table 4.
Table 4 catalyst physico-chemical property
| Project | G | H | I | J |
| Outward appearance | Spherical | Spherical | Spherical | Spherical |
| Size, mm | Φ3-5 | Φ3-5 | Φ3-5 | Φ3-5 |
| Cobalt oxide, % | 1.80 | 1.82 | 1.83 | 1.82 |
| Molybdenum trioxide, % | 9.3 | 9.1 | 9.3 | 9.4 |
| Pore volume, ml/g | 0.40 | 0.38 | 0.48 | 0.52 |
| Specific area, m 2/g | 294 | 275 | 342 | 362 |
| Intensity, N/ | 178 | 189 | 132 | 79 |
| The heap ratio, kg/l | 0.82 | 0.85 | 0.68 | 0.63 |
Embodiment 6:
The preparation method is with embodiment 1, and taking by weighing the 20Kg pore volume is 1.2 milliliters/gram, and specific area is that 438 meters squared per gram, dioxide-containing silica are 2.5% silicone modified aluminum hydroxide solid elastomer powder, places 600 ℃ of roasters, and fast dewatering 1 hour obtains material 1.Take by weighing that pore volume is 0.43 a milliliter/gram after the hydration, specific area is the fast shedding 40Kg of the aluminium hydroxide of 321 meters squared per gram, mixes the ball type carrier of preparation with material 1.The dipping active constituent makes catalyst X, and its physico-chemical property sees Table 5.
Embodiment 7:
The preparation method is with embodiment 1, and taking by weighing the 25Kg pore volume is 1.2 milliliters/gram, and specific area is that 438 meters squared per gram, dioxide-containing silica are 2.5% silicone modified aluminum hydroxide solid elastomer powder, places 600 ℃ of roasters, and fast dewatering 1 hour obtains material 1.Take by weighing that pore volume is 0.43 a milliliter/gram after the hydration, specific area is the fast shedding 25Kg of the aluminium hydroxide of 321 meters squared per gram, mixes the ball type carrier of preparation with material 1.The dipping active constituent makes catalyst Y, and its physico-chemical property sees Table 5.
Embodiment 8:
The preparation method is with embodiment 1, and taking by weighing the 40Kg pore volume is 1.2 milliliters/gram, and specific area is that 438 meters squared per gram, dioxide-containing silica are 2.5% silicone modified aluminum hydroxide solid elastomer powder, places 600 ℃ of roasters, and fast dewatering 1 hour obtains material 1.Take by weighing that pore volume is 0.43 a milliliter/gram after the hydration, specific area is the fast shedding 20Kg of the aluminium hydroxide of 321 meters squared per gram, mixes with material 1.The ball type carrier of preparation, the dipping active constituent makes catalyst Z, and its physico-chemical property sees Table 5.
Table 5 catalyst physico-chemical property
| Project | X | Y | Z |
| Outward appearance | Spherical | Spherical | Spherical |
| Size, mm | Φ3-5 | Φ3-5 | Φ3-5 |
| Cobalt oxide, % | 1.83 | 1.82 | 1.82 |
| Molybdenum trioxide, % | 9.5 | 9.5 | 9.4 |
| Pore volume, ml/g | 0.46 | 0.50 | 0.53 |
| Specific area, m 2/g | 324 | 332 | 348 |
| Intensity, N/ | 126 | 89 | 68 |
| The heap ratio, kg/l | 0.72 | 0.67 | 0.60 |
Claims (10)
1, a kind of Claus tail-gas hydrogenation catalyst, comprise alumina support and group vib or VIII family metal oxide active component, it is characterized in that described alumina support is to be made by the aluminum hydroxide solid elastomer of fast shedding of aluminium hydroxide and silicon modification, the mass ratio of the aluminum hydroxide solid elastomer of fast shedding of aluminium hydroxide and silicon modification is 1: 0.1-2, aluminum hydroxide solid elastomer is with Al
2O
3The quality meter, modifier is with SiO
2The quality meter, modifier SiO
2Amount be Al in the aluminum hydroxide solid elastomer
2O
3The 1-10% of amount.
2, catalyst according to claim 1, the mass ratio that it is characterized in that the aluminum hydroxide solid elastomer of fast shedding of aluminium hydroxide and silicon modification is 1: 0.2-0.5, aluminum hydroxide solid elastomer is with Al
2O
3The quality meter, modifier is with SiO
2The quality meter, modifier SiO
2Amount be Al in the aluminum hydroxide solid elastomer
2O
3The 2-5% of amount.
3, catalyst according to claim 1 and 2, it is characterized in that the fast shedding pore volume of aluminium hydroxide is greater than 0.30 milliliter/gram, specific surface is greater than 260 meters squared per gram, and the silicone modified aluminum hydroxide solid elastomer pore volume is greater than 0.9 milliliter/gram, and specific surface is greater than 350 meters squared per gram.
4, catalyst according to claim 3 is characterized in that the fast shedding pore volume of aluminium hydroxide greater than 0.40 milliliter/gram, and specific surface is greater than 300 meters squared per gram, and the silicone modified aluminum hydroxide solid elastomer pore volume is greater than 1.0 milliliters/gram, and specific surface is greater than 400 meters squared per gram.
5, catalyst according to claim 1 is characterized in that should carrying out fast dewatering before silicone modified aluminum hydroxide solid elastomer uses, and dehydration temperaturre 480-600 ℃, time 0.5-2 hour.
6, catalyst according to claim 1, the preparation that it is characterized in that described carrier be according to usual way by raw material mix with binding agent, moulding, slaking, oven dry, roasting form, the binding agent addition is the 2-10% of aluminium hydroxide gross mass, carrier slaking atmosphere is steam, curing temperature 50-100 ℃, and time 5-12 hour, the bake out temperature of carrier is 80-150 ℃, be 2-20 hour drying time, and sintering temperature is 380-500 ℃, roasting time 2-6 hour.
7, catalyst according to claim 6 is characterized in that described binding agent adopts one or more in water, nitric acid, acetic acid, Ludox, the aluminium colloidal sol.
8, catalyst according to claim 1 is characterized in that in mass percent described group vib metal oxide accounts for the 5-15% of catalyst total amount, and the VIII family metal oxide accounts for the 0.5-5% of catalyst total amount.
9, according to claim 1 or 8 described catalyst, it is characterized in that active component group vib metal is selected from molybdenum or tungsten, VIII family metal is selected from cobalt or nickel.
10, catalyst according to claim 1, the outward appearance that it is characterized in that catalyst is for spherical.
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