CN1836768A - Claus tail gas hydrogenation catalyst - Google Patents

Claus tail gas hydrogenation catalyst Download PDF

Info

Publication number
CN1836768A
CN1836768A CN 200510042213 CN200510042213A CN1836768A CN 1836768 A CN1836768 A CN 1836768A CN 200510042213 CN200510042213 CN 200510042213 CN 200510042213 A CN200510042213 A CN 200510042213A CN 1836768 A CN1836768 A CN 1836768A
Authority
CN
China
Prior art keywords
catalyst
aluminum hydroxide
solid elastomer
gram
pore volume
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN 200510042213
Other languages
Chinese (zh)
Other versions
CN100441274C (en
Inventor
张孔远
刘爱华
燕京
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China Petroleum and Chemical Corp
Original Assignee
China Petroleum and Chemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by China Petroleum and Chemical Corp filed Critical China Petroleum and Chemical Corp
Priority to CNB2005100422131A priority Critical patent/CN100441274C/en
Publication of CN1836768A publication Critical patent/CN1836768A/en
Application granted granted Critical
Publication of CN100441274C publication Critical patent/CN100441274C/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Landscapes

  • Catalysts (AREA)

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

Claus tail-gas hydrogenation catalyst
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.
CNB2005100422131A 2005-03-25 2005-03-25 Claus tail gas hydrogenation catalyst Active CN100441274C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CNB2005100422131A CN100441274C (en) 2005-03-25 2005-03-25 Claus tail gas hydrogenation catalyst

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CNB2005100422131A CN100441274C (en) 2005-03-25 2005-03-25 Claus tail gas hydrogenation catalyst

Publications (2)

Publication Number Publication Date
CN1836768A true CN1836768A (en) 2006-09-27
CN100441274C CN100441274C (en) 2008-12-10

Family

ID=37014359

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB2005100422131A Active CN100441274C (en) 2005-03-25 2005-03-25 Claus tail gas hydrogenation catalyst

Country Status (1)

Country Link
CN (1) CN100441274C (en)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009039019A2 (en) * 2007-09-17 2009-03-26 Shell Oil Company A catalyst composition useful in the catalytic reduction of sulfur compound contained in a gas stream and a method of making and using such composition
CN102029165A (en) * 2010-11-09 2011-04-27 中国海洋石油总公司 Method for preparing ozone catalytic oxidation catalyst for treating coking wastewater
CN102380311A (en) * 2010-09-01 2012-03-21 中国石油化工股份有限公司 Gasoline adsorption desulfuration regeneration smoke treatment method and tail gas hydrogenation catalyst preparation method thereof
CN103521203A (en) * 2012-06-12 2014-01-22 中国石油化工股份有限公司 Aluminum oxide-based sulfur recovery catalyst and preparation method thereof
CN103611544A (en) * 2013-12-05 2014-03-05 湖北双雄催化剂有限公司 Preparation method capable of improving low-temperature activity of low-pressure cobalt-molybdenum sulfur-tolerant shift catalyst
CN104302388A (en) * 2012-04-23 2015-01-21 雷普索尔有限公司 Catalyst for the selective oxidation of sulphur compounds
CN105293443A (en) * 2014-06-06 2016-02-03 中国石油化工股份有限公司 Method for decreasing flue gas SO2 emission concentration of sulphur apparatus
CN115228480A (en) * 2021-04-23 2022-10-25 中国石油天然气股份有限公司 Hydro-hydrolysis catalyst and preparation method thereof

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101879451B (en) * 2009-05-07 2013-06-12 中国石油化工股份有限公司 Low-temperature Claus tail-gas hydrogenation catalyst and preparation method thereof

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4243647A (en) * 1976-06-28 1981-01-06 Union Oil Company Of California Process for removal of hydrogen sulfide from gas streams
US4473541A (en) * 1983-05-31 1984-09-25 Standard Oil Company (Indiana) Low water content sulfur recovery process
KR940007361B1 (en) * 1991-12-05 1994-08-16 포항종합제철 주식회사 Process for tail gas treatment
JP3332964B2 (en) * 1992-10-19 2002-10-07 日揮株式会社 Hydrotreating method for sulfur compound containing gas
EP1090675A1 (en) * 1999-09-30 2001-04-11 Gastec N.V. Process for the removal of sulphur compounds from gases
EP1295848A1 (en) * 2000-09-12 2003-03-26 Gastec N.V. Process for the selective oxidation of hydrogen sulphide to elemental sulphur
EP1186571A1 (en) * 2000-09-12 2002-03-13 Gastec N.V. Process for the selective oxidation of hydrogen sulphide to elemental sulphur
CN100441272C (en) * 2002-11-06 2008-12-10 中国石油化工股份有限公司 Catalyzer for hydrogenation on tail gas of sulphur and its prepn. method

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101835537B (en) * 2007-09-17 2013-05-22 国际壳牌研究有限公司 A catalyst composition useful in the catalytic reduction of sulfur compound contained in a gas stream and a method of making and using such composition
WO2009039019A3 (en) * 2007-09-17 2009-05-07 Shell Oil Co A catalyst composition useful in the catalytic reduction of sulfur compound contained in a gas stream and a method of making and using such composition
US8609051B2 (en) 2007-09-17 2013-12-17 Shell Oil Company Catalyst composition useful in the catalytic reduction of sulfur compound contained in a gas stream and a method of making and using such composition
WO2009039019A2 (en) * 2007-09-17 2009-03-26 Shell Oil Company A catalyst composition useful in the catalytic reduction of sulfur compound contained in a gas stream and a method of making and using such composition
US8142748B2 (en) 2007-09-17 2012-03-27 Shell Oil Company Catalyst composition useful in the catalytic reduction of sulfur compound contained in a gas stream and a method of making and using such composition
CN102380311A (en) * 2010-09-01 2012-03-21 中国石油化工股份有限公司 Gasoline adsorption desulfuration regeneration smoke treatment method and tail gas hydrogenation catalyst preparation method thereof
CN102380311B (en) * 2010-09-01 2013-12-25 中国石油化工股份有限公司 Gasoline adsorption desulfuration regeneration smoke treatment method and tail gas hydrogenation catalyst preparation method thereof
CN102029165B (en) * 2010-11-09 2012-10-17 中国海洋石油总公司 Method for preparing ozone catalytic oxidation catalyst for treating coking wastewater
CN102029165A (en) * 2010-11-09 2011-04-27 中国海洋石油总公司 Method for preparing ozone catalytic oxidation catalyst for treating coking wastewater
CN104302388A (en) * 2012-04-23 2015-01-21 雷普索尔有限公司 Catalyst for the selective oxidation of sulphur compounds
CN103521203A (en) * 2012-06-12 2014-01-22 中国石油化工股份有限公司 Aluminum oxide-based sulfur recovery catalyst and preparation method thereof
CN103611544A (en) * 2013-12-05 2014-03-05 湖北双雄催化剂有限公司 Preparation method capable of improving low-temperature activity of low-pressure cobalt-molybdenum sulfur-tolerant shift catalyst
CN103611544B (en) * 2013-12-05 2015-04-22 湖北双雄催化剂有限公司 Preparation method capable of improving low-temperature activity of low-pressure cobalt-molybdenum sulfur-tolerant shift catalyst
CN105293443A (en) * 2014-06-06 2016-02-03 中国石油化工股份有限公司 Method for decreasing flue gas SO2 emission concentration of sulphur apparatus
CN115228480A (en) * 2021-04-23 2022-10-25 中国石油天然气股份有限公司 Hydro-hydrolysis catalyst and preparation method thereof

Also Published As

Publication number Publication date
CN100441274C (en) 2008-12-10

Similar Documents

Publication Publication Date Title
CN1836768A (en) Claus tail gas hydrogenation catalyst
CN102029140B (en) Desulfurizing agent with nuclear/shell structure and preparation method
CN110639466B (en) Dearsenic adsorbent and preparation method thereof
CN102899083B (en) Ultra-deep combined desulphurization method for full-fraction FCC gasoline
CN107413293A (en) A kind of desulfurizing agent and preparation method and application
CN1498674A (en) Catalyzer for hydrogenation on tail gas of sulphur and its prepn. method
CN109395770B (en) Iron-based hydrogenation catalyst and preparation method thereof
CN103028368A (en) Gas desulfurization sorbent and preparation method thereof and desulfurization method of sulfur-containing gas
CN103028363B (en) The sulfur method of gas sweetening adsorbent and preparation method thereof and sulfurous gas
CN1990827A (en) Catalytic cracking desulfurizing assistant agent
CN105289632B (en) A kind of method of desulfurization of hydrocarbon oil catalyst and preparation method thereof and desulfurization of hydrocarbon oil
CN1089275C (en) Preparation of pseudo-thin diasphore and gamma-alumina
CN105903324A (en) Copper oxide loaded active carbon desulfurizing agent and preparation process thereof
CN1123713A (en) Alumina-based catalyst for the treatment of gases containing sulphur compounds, use of these catalysts for the treatment and processes for treatment of the said gases
CN1340601A (en) Aromatizing catalyst for light hydrocarbon and its preparing process
CN101058748A (en) Diesel oil hydrofining catalyst containing phosphorous or molecular sieve and preparation method thereof
CN1621134A (en) Method for preparing sulphur tail gas hydrogenation catalyst
CN102294224A (en) Hydrocarbon oil desulfurization adsorbent and preparation method and application thereof
CN112973706B (en) Nickel-based catalyst and preparation and application thereof
CN105618070B (en) A kind of preparation method of high activity desulfurization catalyst of flue gas
CN105289681B (en) A kind of method of desulfurization of hydrocarbon oil catalyst and preparation method thereof and desulfurization of hydrocarbon oil
CN103028367B (en) Gas desulfurization adsorbent, preparation method thereof and desulfurization method for sulfur-containing gas
CN1361229A (en) Selectively mercaptan-eliminating catalyst for aviation fuel and its prepn
RU2812535C1 (en) Catalyst for hydrogenation and hydrolysis of sulfur compounds in waste gases of claus process and method of its use
CN109351326A (en) A kind of renewable mercury removal agent and preparation method thereof for natural gas

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant