CN1498674A - Catalyzer for hydrogenation on tail gas of sulphur and its prepn. method - Google Patents
Catalyzer for hydrogenation on tail gas of sulphur and its prepn. method Download PDFInfo
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- CN1498674A CN1498674A CNA021356998A CN02135699A CN1498674A CN 1498674 A CN1498674 A CN 1498674A CN A021356998 A CNA021356998 A CN A021356998A CN 02135699 A CN02135699 A CN 02135699A CN 1498674 A CN1498674 A CN 1498674A
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Abstract
A hydrocatalyst for treating claus tail gas is prepared from the silicon oxide modified gamma-Al2O3 as carrier and the metals chosen from the families VIB and VIII through immersion. Its advantages are stable and high activity to hydrogenolyze the organic sulfur and hydrolyze CS2 and COS, low energy consumption, and simple preparing process.
Description
Invention field
The present invention relates to a kind of Claus catalyzer for hydrogenation on tail gas and preparation method thereof, more particularly, relate to a kind of silica modified γ-AL
2O
3Be carrier, cobalt, molybdenum are Claus catalyzer for hydrogenation on tail gas of active constituent and preparation method thereof.
Background technology
Along with the strictness day by day of environmental regulation and the further enhancing of people's environmental consciousness, also more and more stricter to the requirement of sulfur-containing compound discharge standard in PETROLEUM PROCESSING and the petrochemical plant.In order to satisfy the requirement of new environmental protection standard, oil plant and Gas Purification Factory sulfur recovery facility total sulfur recovery must reach more than 99.70%, and in order to satisfy above-mentioned total sulfur recovery, most of sulfur recovery unit has all adopted the reduction absorption technique.Be that the sulfur-bearing sour gas is after secondary Crouse transforms, enter hydrogenation reactor, under the effect of hydrogenation catalyst, the 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 key technology that influences this technology total sulfur recovery is to adopt highly active sulfur-containing compound (or elemental sulfur) hydrogenation catalyst and CS
2With the COS hydrolyst.Because the suitable high temperature of hydrogenation reaction carries out (greater than 300 ℃), and CS
2Carry out (less than 250 ℃) with the suitable low temperature of COS hydrolysis, thus present industrial employing two-stage process, i.e. the hydrogenation reactor top hydrolyst (low temperature) of packing into, the bottom hydrogenation catalyst (high temperature) of packing into.Disclose a kind of sulfur-bearing Claus tail gas hydrogenation treatment process and catalyst as Japan Patent on May 10th, 1994 (patent No. JP06127907 A2), during two kinds of catalyst of employing were packed same reactor in this patent, top was MoO
3/ TiO
2Catalyst, wherein MoO
3Content reaches 16%; The bottom is Co-Mo/AL
2O
3Catalyst, wherein MoO
3Content 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 active component greater than 25% with nickel, molybdenum, needs and COS, CS
2Hydrolytic reagent (K/TiO
2) use with being loaded in the reactor.
Summary of the invention
The purpose of this invention is to provide a kind of claus reaction end gas hydrogenation catalyst and preparation method thereof, it not only has good organic sulfur hydrogenolysis activity, and has good CS
2With the COS hydrolysing activity.
Cobalt oxide and molybdenum oxide content are respectively 1～5% (m/m) in the claus reaction end gas hydrogenation catalyst of the present invention, preferably 2～4 (m/m) and 5～15 (m/m) 8～13% (m/m) preferably; SiO in the carrier
2Content is 1～20% (wt), 2～10% (m/m) preferably, and all the other are γ-Al
2O
3
The catalyst major technique feature of the present invention's preparation is:
1, the pore volume of carrier should be worked energetically 0.40ml/g, more preferably greater than 0.45ml/g; Specific area should be greater than 250m
2/ g is more preferably greater than 300m
2/ g; The aperture is more than 70% at the pore volume between the 2.5-5.0nm, and is best more than 80%; The most probable radius is 2.0～8.0nm, is preferably 3.0～6.0nm; The carrier outward appearance is preferably clover or bunge bedstraw herb type.
2, active component be the group vib element and (or) VIII family metallic element, its percetage by weight in catalyst is group vib metal oxide content 5-15%, is preferably 8-13%.VIII family metal oxide content 1-5% (m/m) is preferably 2-4%.
3, the support modification agent becomes in the glue process with the form adding of sodium metasilicate or in the batch mixing process of preparation carrier at the preparation aluminum hydroxide solid elastomer, form with Ludox adds, its content is to make the weight of final silica account for the 1-20% of vehicle weight, is preferably 2-10%.
4, the group vib metallic element is molybdenum and tungsten, preferred molybdenum, and precursors is an ammonium molybdate, VIII family metallic element is cobalt and nickel, preferred cobalt, precursors is cobalt nitrate or cobalt acetate.
Preparation of catalysts method of the present invention comprises the steps:
A, choose suitable aluminum hydroxide solid elastomer, add the binding agent, expanding agent of proportional quantity and silica sol modified dose, perhaps in the one-tenth glue process of preparation aluminum hydroxide solid elastomer, the sodium metasilicate that adds proportional quantity, again aluminum hydroxide solid elastomer is mixed with binding agent, expanding agent, said mixture is mixed pinch, moulding, after the drying, in 480～600 ℃ of following roastings, can make the γ-Al of silicon oxide-containing
2O
3Carrier.
B, employing equal-volume single-steeping method are with the silica modified γ-Al that obtains among the hydrogenation activity component maceration extract impregnation steps A
2O
3Carrier, dry back can make catalyst of the present invention in 480～550 ℃ of following roastings.
More specifically, catalyst of the present invention can adopt following steps preparations (wherein the hydrogenation activity component is represented with cobalt, molybdenum respectively):
1, choosing pore volume is 0.7～1.0 milliliter/gram, specific surface is the aluminum hydroxide solid elastomer of 300～450 meters squared per gram, binding agent (as water, nitric acid, acetate, oxalic acid) with conventional proportional quantity, and expanding agent (as polyvinyl alcohol, poly amic acid, field mountain valley with clumps of trees and bamboo powder, citric acid etc.) mixing, add Ludox by proportioning then.Perhaps adopt in the one-tenth glue process of preparation aluminum hydroxide solid elastomer, add the method for the sodium metasilicate of proportional quantity, be about to be diluted to 10～35g Al
2O
3The sodium aluminate solution of/L places in the glue jar, and 0～25 ℃ of control temperature, feeding concentration are 30～40% CO
2Gas carries out neutralization reaction, slowly adds sodium metasilicate simultaneously, makes the content of final silica in carrier reach 1～20 weight %, and control glue PH=10～12 o'clock stops into glue.Then through routine filtration, washing, drying. be crushed to about 180 orders, make aluminum hydroxide solid elastomer.With the aluminum hydroxide solid elastomer that makes like this, again with the binding agent (as water, nitric acid, acetate, oxalic acid) of conventional proportional quantity, and expanding agent (as polyvinyl alcohol, poly amic acid, field mountain valley with clumps of trees and bamboo powder, citric acid etc.) mixes.
Said mixture mixed pinch, extruded moulding, again in 110～150 ℃ of oven dry 2～4 hours, in 480～600 ℃ of roastings 4～8 hours, can make and contain 1～20% (m/m), preferably γ-the Al of 2～10% (m/m) silica
2O
3Carrier.
2, get the ammoniacal liquor of convention amount 22～28% concentration, the cobalt salt that adds proportional quantity, as cobalt nitrate or cobalt acetate, the ethylenediamine that under constantly stirring, adds people's convention amount, make it to form stable cobalt ethylenediamine complex compound, the amount that makes ethylenediamine is 1/50～1/7 of cobalt nitrate or a cobalt acetate weight, is preferably 1/20～1/15, the ammonium molybdate that adds proportional quantity then is stirred to dissolving fully.
Get isopyknic above-mentioned co-impregnated solution, the carrier that obtains in the impregnation steps 1 2～4 hours is in 110～150 ℃ of oven dry 2～6 hours, 480～550 ℃ of following roastings 3～8 hours.Wherein cobalt oxide and molybdenum oxide content are respectively 1～5% in catalyst weight, and preferably 2～4% and 5～15%, preferably 8～13%.Make Claus catalyzer for hydrogenation on tail gas of the present invention like this.
Catalyst of the present invention is because its carrier has pore volume, specific area is big, and the characteristics that pore-size distribution is concentrated can make the active component high degree of dispersion, not only have good organic sulfur hydrogenolysis activity, and has good CS
2With the COS hydrolysing activity; Outward appearance adopts clover or bunge bedstraw herb type, and bed resistance reduces, the side pressure strength height, wear away low, water-fast Heat stability is good, anti-efflorescence ability is strong, heap is than gently, same reactor can reduce the catalyst loading amount.
The specific embodiment
Embodiment 1 (embodiment 1-4 is the preparation of carrier)
With concentration is 35Kg Al
2O
3The sodium aluminate solution of/L places in the glue jar, and feeding concentration is the CO of 40 volume %
2Gas, nine water sodium metasilicate by every liter of solution adding 3.4Kg make carrier contain SiO
22% (weight) during control glue PH=10, stops into glue.Filter then, spend deionised water, after drying, be crushed to about 180 orders, making pore volume is 0.88 milliliter/gram, and specific area is the aluminum hydroxide solid elastomer of 395 meters squared per gram.
The nitric acid of 4.3Kg 65 weight % is dissolved in 100 liters the deionized water, after stirring, adds in the above-mentioned aluminum hydroxide solid elastomer powder of 100Kg and be mixed, add 5Kg field mountain valley with clumps of trees and bamboo powder again, mix behind the mixing and pinch 3 times, be extruded into Φ 3mm clover bar, in 110 ℃ of oven dry 4 hours, SiO was made in 550 ℃ of roastings 4 hours
2-γ-Al
2O
3Carrier (A), its character sees Table 1.
Embodiment 2
The nitric acid of 4.3Kg 65 weight % is dissolved in 100 liters the deionized water, choosing the 100Kg pore volume is 0.80 milliliter/gram, and specific surface is the aluminum hydroxide solid elastomer of 305 meters squared per gram, is mixed, and adds 5Kg field mountain valley with clumps of trees and bamboo powder again, adds SiO behind the mixing
2Content is the Ludox 4.8Kg of 25-26%, mixes to pinch 3 times, is extruded into Φ 3mm clover bar, and in 110 ℃ of oven dry 4 hours, SiO was made in 550 ℃ of roastings 4 hours
2-γ-Al
2O
3Carrier (B), its character sees Table 1.
Embodiment 3
The preparing carriers method is with example 1, but the amount of nine water sodium metasilicate is 8.7Kg, makes SiO
2-γ-Al
2O
3Carrier (C), its character sees Table 1.
Embodiment 4
The preparing carriers method is with example 2, but the amount of Ludox is 24Kg, makes SiO
2-γ-Al
2O
3Carrier (D).
The physico-chemical property of table 1 carrier
| Bearer number | ??SiO 2Content, % | Pore volume (ml/g) | Specific area (m 2/g) | Intensity N/cm | 2.5-5.0nm the hole account for the percentage of total pore volume) | Most probable radius (nm) |
| ????A | ????2 | ????0.59 | ????307 | ??182 | ?????????92％ | ????4.0 |
| ????B | ????2 | ????0.48 | ????256 | ??203 | ?????????88％ | ????4.3 |
| ????C | ????5 | ????0.66 | ????397 | ??236 | ?????????94％ | ????4.0 |
| ????D | ????10 | ????0.56 | ????304 | ??347 | ?????????81％ | ????4.9 |
Embodiment 5
Preparation of Catalyst:
18.5 gram cobalt nitrates are joined in the ammoniacal liquor of 90ml 25-28%, stir, add 1.0 milliliters of ethylenediamines, add 20.2 gram ammonium molybdates then, constantly be stirred to and form red sauce solution, respectively the carrier among the 100 gram example 1-4, was dried 4 hours in 110 ℃ after 2 hours with this maceration extract dipping, in 500 ℃ of roastings 4 hours, just make CO-Mo/SiO of the present invention
2-γ-Al
2O
3Catalyst (A-1 to D-1), wherein molybdenum oxide (MoO
3) content is 10.5% (m/m), cobalt oxide (CoO) content is 2.49% (m/m).
Embodiment 6
Catalyst hydrogenation and hydrolysing activity:
Get 800.0 milliliters of catalyst in the example 5, granularity is 3-5mm, is loaded in the industrial side line reactor, adopts 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 400h
-1, hydrogen content is 0.5-8% (v/v) in the unstripped gas.
Sulfuration switches to Claus tail gas after finishing.At 260 ℃ of reaction temperatures, volume space velocity 2500h
-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:
The catalytic reactor inlet gas is formed, and (v/v) the % reactor outlet gas is formed, (v/v) %
Agent H
2S COS SO
2H
2CO
2H
2S COS SO
2H
2CO
2
A-1????0.45????0.03????0.96????4.90????-????1.54????-????-????2.86????-
B-1????0.63????0.02????1.09????4.90????-????1.87????-????-????2.46????-
C-1????0.62????0.03????1.08????5.62????-????1.94????-????-????3.70????0.09
D-1????0.63????0.02????0.86????5.05????-????1.65????-????-????2.72????-
Embodiment 7
The catalyst desulfurizing activity:
Get catalyst in the example 5 on industrial side line device, after the method sulfuration of implementing in 6, temperature is transferred to 300 ℃, volume space velocity volume space velocity 3800h
-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:
The catalytic reactor inlet gas is formed, and (v/v) the % reactor outlet gas is formed, (v/v) %.
Agent H
2S COS SO
2H
2CO
2H
2S COS SO
2H
2CO
2
A-1????0.67????0.03????0.89????5.08????0.6????1.82????-????-???1.84???0.80
B-1????0.61????0.03????0.92????6.17????0.4????2.12????-????-???2.62???0.60
C-1????0.72????0.02????0.95????5.42????0.5????2.21????-????-???2.31???1.10
D-1????0.66????0.02????0.88????5.32????0.3????1.86????-????-???2.80???0.54
Claims (10)
1. Claus catalyzer for hydrogenation on tail gas is with silica modified γ-Al
2O
3Be carrier, support the hydrogenation activity component, the specific area that it is characterized in that carrier is greater than 250 meters squared per gram, and pore volume is greater than 0.40 milliliter/gram, and pore-size distribution is to account for more than 70% of total pore volume between the 2.5-5.0nm, and the most probable radius is 2.0～8.0nm.
2. press claim 1 described catalyst, it is characterized in that the outward appearance of carrier is clover or bunge bedstraw herb type.
3. press claim 1 described catalyst, the content that it is characterized in that silica in the described carrier is 1～20 weight %.
4. press claim 1 described catalyst, it is characterized in that the hydrogenation activity component is group vib and group VIII metal, content accounts for the 5-15% of catalyst weight for the group vib metal oxide, and the VIII family metal oxide accounts for the 1-5% of catalyst weight.
5. press claim 4 described catalyst, it is characterized in that the group vib metal oxide accounts for the 8-13% of catalyst weight, the VIII family metal oxide accounts for the 2-4% of catalyst weight.
6. press claim 4 or 5 described catalyst, it is characterized in that the group vib metal is a molybdenum, VIII family metal is a cobalt.
7. claim 1 a described Preparation of catalysts method comprises the steps:
A, choose aluminum hydroxide solid elastomer, add the binding agent, expanding agent of proportional quantity and silica sol modified dose, perhaps in the one-tenth glue process of preparation aluminum hydroxide solid elastomer, the sodium metasilicate modifier that adds proportional quantity, again aluminum hydroxide solid elastomer is mixed with binding agent, expanding agent, said mixture is mixed pinch, moulding, after the drying, in 480～600 ℃ of following roastings, can make the γ-Al of silicon oxide-containing
2O
3Carrier.
B, employing equal-volume single-steeping method are with the silica modified γ-Al that obtains among the hydrogenation activity component maceration extract impregnation steps A
2O
3Carrier makes dry back in 480～550 ℃ of following roastings, can make catalyst of the present invention.
8. press claim 7 described preparation methods, the expanding agent in the steps A is the volatilizable organic matters of roasting process such as polyethylene, polyacrylamide, sesbania powder or citric acid, and its addition is the 4-6% of vehicle weight;
9. press claim 7 described preparation methods, the binding agent in the steps A is water, nitric acid, acetate or oxalic acid, and its addition is the 3-6% of vehicle weight.。
10. press claim 7 described methods, it is characterized in that in the steps A the aluminum hydroxide solid elastomer pore volume greater than 0.70 milliliter/gram, specific surface is greater than 300 meters squared per gram.
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Family Cites Families (4)
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-
2002
- 2002-11-06 CN CNB021356998A patent/CN100441272C/en not_active Expired - Lifetime
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| CN112973713B (en) * | 2019-12-16 | 2023-11-03 | 山西腾茂科技股份有限公司 | Hydrofining catalyst and preparation method thereof |
| CN112870964A (en) * | 2020-12-28 | 2021-06-01 | 阜阳莱纳环保科技有限公司 | Hydrogenation catalyst and application thereof in treating sulfur-containing waste gas |
| CN112604709A (en) * | 2020-12-28 | 2021-04-06 | 阜阳莱纳环保科技有限公司 | Hydrogenation catalyst for treating sulfur-containing waste gas and application thereof |
| CN112604709B (en) * | 2020-12-28 | 2023-09-01 | 乐山绿典节能环保科技有限公司 | Hydrogenation catalyst for sulfur-containing waste gas treatment and application thereof |
| CN112870964B (en) * | 2020-12-28 | 2023-12-22 | 大连安泰化工有限公司 | Hydrogenation catalyst and application thereof in sulfur-containing waste gas treatment |
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| CN100441272C (en) | 2008-12-10 |
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