CN101745399A - Selective reduction catalyst used for recovering sulfur, preparation method and application thereof - Google Patents

Selective reduction catalyst used for recovering sulfur, preparation method and application thereof Download PDF

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Publication number
CN101745399A
CN101745399A CN200810237813A CN200810237813A CN101745399A CN 101745399 A CN101745399 A CN 101745399A CN 200810237813 A CN200810237813 A CN 200810237813A CN 200810237813 A CN200810237813 A CN 200810237813A CN 101745399 A CN101745399 A CN 101745399A
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catalyst
selective reduction
carrier
hours
sulfur
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胡文宾
崔传义
邵志辉
王强
朱敦富
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ZHEJIANG SHENGYI ENVIRONMENT PROTECTION TECHNOLOGY Co Ltd
SHANDONG XUNDA CHEMICAL GROUP CO Ltd
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ZHEJIANG SHENGYI ENVIRONMENT PROTECTION TECHNOLOGY Co Ltd
SHANDONG XUNDA CHEMICAL GROUP CO Ltd
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Abstract

The invention introduces a selective reduction catalyst used for recovering sulfur, a preparation method and an application thereof, which belong to the technical field of the recovery of the sulfur. The invention has the main principle that the selective reduction catalyst is adopted in a hydrogenation reduction reactor to selectively catalyze and reduce SO2 into elemental sulfur instead of H2S, and then the generated elemental sulfur is delivered into a liquid sulfur storage tank after the elemental sulfur is cooled. The invention solves the defect that the traditional tail gas hydrogenation reactor does not generate the sulfur, enhances the one-way total sulfur recovery efficiency of a device, lowers the operation temperature of the hydrogenation reduction reactor and saves the energy consumption and the equipment investment.

Description

A kind of selective reduction catalyst used for recovering sulfur and method for making thereof and application
Technical field
The invention belongs to the sulphur recovery technical field, be specifically related to a kind of selective reduction catalyst used for recovering sulfur and method for making thereof and application.
Background technology
Sulfide in crude oil or the coal is converted into H in process 2S, and H 2S is an extremely toxic substance, and human body and environment are had great toxic action, must carry out harmless treatment, and the only technology of corresponding employing is exactly recovery technology of sulfur.The sour gas of oil plant is mainly derived from devices such as catalysis drying gas desulfurization, the desulfurization of coking dry gas, sewage gas stripping tower gas, hydro-refining unit desulfurization.The main work flow of the sour gas of oil plant is:
Sulphur → PETROLEUM PROCESSING in the crude oil (normal decompression) → gasoline kerosene diesel oil → hydrofinishing → H 2S → sulphur recovery → sulphur
Be in the chemical plant of raw material with the coal, the work flow of sour gas mainly is coal → Coal Chemical Industry → desulfurization → H 2S → sulphur recovery → sulphur.
Industry generally adopts the improvement claus process to handle the H that contains of generations such as oil plant, chemical plant 2The sour gas of S, Recovered sulphur is also protected environment.Its basic principle is as follows:
Figure G2008102378137D0000011
Figure G2008102378137D0000012
Because the existence of hydro carbons under the hot conditions of combustion furnace, inevitably has a spot of organic sulfur compound CS in the sour gas 2Generate with COS, therefore must be removed by the tempreture organic sulphur hydrolysis reaction at catalytic reactor:
Figure G2008102378137D0000013
Figure G2008102378137D0000014
The basic technology type of claus reaction has three kinds: direct current method, shunting and sulfur cycle method: direct current method be sour gas all by combustion furnace and waste heat boiler, in combustion furnace, generate a large amount of sulphur; Shunting is to have only 1/3rd sour gas to burn into SO by combustion furnace 2, before converter, being mixed into converter with remainder, the sulphur that generates in the stove is seldom; The sulfur cycle method be sour gas by combustion furnace, and the sulphur generation SO that in stove, burn 2And before first converter with contain H 2The sour gas mixing of S is reacted.
The world has proposed more and more higher requirement to the demand of clean fuel and from the pressure of the environmental regulation of increasingly stringent to the total sulfur recovery of sulfur recovery facility, on the one hand, because the H of the increase by-product of oil plant working ability 2S is more and more, and the device discharge capacity that government department requires is more and more lower, improves the total sulfur recovery of device when this just requires to increase the sulfur recovery facility disposal ability to satisfy double requirements.
State Bueau of Environmental Protection has formulated strict more discharge standard of air pollutants (GB16297-1996) and has stipulated since mandatory enforcement on January 1 in 1997.GB16297 is to SO 2Strict regulations have been made in discharging, new pollution sources SO 2≤ 960mg/m 3(336ppmv), existing pollution sources SO 2≤ 1200mg/m 3(420ppmv), and to the sulfide emission amount also made regulation.By this standard, require oil plant and chemical plant sulphur recovery total sulfur recovery will reach 99.7～99.9%.Claus plant has only the reduction adopted to absorb the requirement that tail gas treatment process just can reach above-mentioned environmental protection standard.
Traditional claus process mainly comprises equipment compositions such as sour gas combustion furnace, waste heat boiler, two or three catalytic reactors and condenser, trap.The total sulfur conversion ratio can reach 94～97% behind general second reactor.The catalyst of corresponding employing mainly contains activated alumina catalyst, auxiliary agent type aluminium oxide catalyst and titanium deoxide catalyst etc.
In order to satisfy higher environmental requirement, must carry out further purified treatment to the tail gas that Cross unit is discharged.As shown in Figure 1, the technology of past employing mainly contains low-temperature Claus technology, super claus process, tail gas hydrogenation reducing process etc.But it is inaccurate to have only the tail gas hydrogenation reducing process can satisfy the strictest environmental protection.Total sulfur recovery can reach more than 99.8%.The cardinal principle of tail gas hydrogenation reducing process is to adopt hydrogen with the non-H in the sulfur recovery facility tail gas 2The sulfur-containing compound of S such as SO 2/ COS/CS 2/ S etc. all are hydrogenated to H 2S, then by MDEA with H 2The sour gas combustion furnace that turns back to sulfur recovery facility after S absorption and the desorb carries out further sulphur recovery.The tail gas of discharging from the top, absorption tower only contains the sulfide of trace, by entering atmosphere behind the incinerator high temperature incineration.SO in the flue gas 2Discharge capacity less than 960mg/m 3, satisfy the emission request of GB16297-1996.
That the tail gas hydrogenation reduction reactor adopts is common CoO/MoO/Al 2O 3Hydrogenation catalyst, inlet temperature are 280～300 ℃, and reactor batch temperature is generally 300～330 ℃.
Summary of the invention
The present invention has introduced a kind of selective reduction sulphur recovery technology newly developed, and its cardinal principle is to adopt selective reduction catalyst with SO in the hydrogenation reduction device 2SCR is elemental sulfur rather than H 2S will send into the molten sulfur storage tank after the elemental sulfur cooling that generate then.
The following technical scheme of the concrete employing of the present invention:
Catalyst of the present invention is to be prepared from by traditional dipping or the mixed method of pinching, at first with the predecessor wiring solution-forming of active constituent, then zirconia, aluminium oxide, silica or titanium dioxide carrier are dipped in wherein and extremely flood evenly, perhaps adopt predecessor and the mixed way of pinching of zirconia, aluminium oxide or titanium oxide are prepared.For guaranteeing dipping evenly, solution is general excessive 20～30% in the preparation process, and the dipping surplus liquid in back fully inclines to, and carries out the drying and roasting catalyst that gets product after then the catalyst sample room temperature being dried.
Wherein the carrier of Cai Yonging mainly contains aluminium oxide, silica, zirconia and titanium oxide and adds suitable binding agent and form, and the specific area of active oxidation alumina support is 100～600m 2/ g is preferably 320～400m 2/ g, pore volume is 0.30～1.2ml/g, is preferably 0.4～0.8ml/g.The activated alumina that the crystal formation of activated alumina is preferably γ or ρ type or meets other suitable crystal formations that These parameters requires also can use.Average crushing strength is in 80～300 newton/best.
Be suitable for starting material of the present invention false boehmite, boehmite, Bayer process gibbsite or a gibbsite or β gibbsite and other forms of aluminium hydroxide are arranged.When to pass through NaAlO 2When fast the false boehmite that obtains of neutralization is as starting material with acid aluminium salt, need remove residual sodium oxide molybdena by washing repeatedly.Need to add the SiO in the sodalite increase aluminium oxide simultaneously 2Content helps to improve catalyst heat endurance at high temperature.Under 400～500 ℃ of conditions, keep at last and aluminium oxide was activated in 2～4 hours.
The specific area of the Zirconia carrier that adopts is 100～300m 2/ g is preferably in 250～300m 2/ g, pore volume is at 0.2～0.5ml/g, the mechanical strength that is preferably in the Zirconia carrier that 0.3～0.4ml/g. adopts can be selected cylindrical bar shaped, clover or bunge bedstraw herb or six leaf swath shapes in 100～200 newton/best, also can be spherical or cylindrical.
The titanium dioxide carrier that adopts mainly is by being converted into TiO after roasting or the drying 2Material be prepared from.These materials mainly contain titanium sulfate, titanyl sulfate, titanium tetrachloride, tetra isopropyl titanium, metatitanic acid colloidal sol or metatitanic acid gel etc.At TiO 2In the preparation process of carrier, take specific process control TiO 2The grain size and the crystalline state of particle are extremely important.For example, with Ti 2(SO 4) 2Solution is feedstock production TiO 2The time, the PH of the temperature of the adding speed of the concentration of control solution, precipitating reagent concentration, precipitating reagent and adding mode, heating and mixing speed, solution etc. are very important.With TiO 2Be the carrier of main component, adopt traditional extrusion or spin forming technique, mechanical strength can not satisfy industrial instructions for use.
Therefore in order to improve intensity, adopt three kinds of methods usually: the one, the compression molding technology, the 2nd, add binding agent high-temperature roasting simultaneously, the 3rd, not adding additives and directly high-temperature roasting.If adopt the compression molding technology, must increase pressure, reduced TiO thus 2The pore volume of carrier, and cause the pore structure of carrier to be difficult to control has adverse influence to the load capacity of carrier and activity of such catalysts and selectivity.If adopt to add the method for binding agent, can use Ludox, boric acid, aluminium colloidal sol, nitric acid etc., although can improve the intensity of carrier by adding binding agent, binding agent is easily and TiO in the drying and roasting process 2Predecessor generate solid solution or be difficult for determining the composite oxides of structure, stopped up the duct of carrier and covered the activity of such catalysts surface, changed the physico-chemical property of carrier and catalyst.Adopt the technology of high-temperature roasting also can cause carrier to undergo phase transition and the growing up of ion crystal grain, influence activity of such catalysts.
The predecessor of the silica that adopts can be a sodium metasilicate, also can adopt other alumino-silicates, all can use as long as can be converted into the material of SiO2 after the roasting.Also can directly adopt the silica product of spherical or other shapes of typing, the general SiO that requires employing 2Specific area 100～400m 2/ g, average crushing strength be 80～300 newton/.
The present invention has mainly introduced a kind of selective reduction sulphur recovery technology and employed SO 2Selective reduction is the catalyst of elementary sulfur, method provided by the invention can produce that a kind of what have bigger serface, large pore volume and have good mechanical strength, wear hardness is the composite oxide carrier of raw material with zirconia, aluminium oxide, titanium oxide, silica etc., every physical and chemical performance index of carrier can simply be controlled and change, thus by adding CoO/MoO 3/ NiO/WO 3The selective hydrogenation reducing catalyst of isoreactivity component preparation is active high, and selectivity is good, can satisfy the instructions for use of selective reduction sulphur recovery technology.
The main flow process of selective reduction sulphur recovery technology of introduction of the present invention comprises sour gas combustion furnace, waste heat boiler, first catalytic reactor, second catalytic reactor, SO 2Selective reduction reactor and remaining H2S absorption tower and regenerator etc.The hot mode again of first catalytic reactor wherein, second catalytic reactor and tail gas hydrogenation reactor inlet can be selected variety of ways such as online heating furnace, heat exchanger, hot fusion.The inlet temperature of first, second catalytic reactor is 200～300 ℃, and the inlet temperature of tail gas hydrogenation reduction reactor is 160～300 ℃.The outlet of tail gas hydrogenation reduction reactor does not contain SO 2, COS/CS 2, only contain elemental sulfur and H 2Two kinds of sulfide of S.By behind condenser and the sulphur that the trap branch goes, enter in the air-flow of tail gas absorber and do not contain SO 2And elemental sulfur.Technology of the present invention also can adopt one or more converters, and this can determine according to the actual conditions of owner and sour gas.
Technology of the present invention also is applicable to handles H 2S concentration also can not used combustion furnace less than 20% low concentration sour gas, adopts the direct oxidation reactor to replace combustion furnace to operate, and the operating temperature of direct oxidation reactor can be controlled at below 600 ℃.Subsequent technique is basic identical.
Technology of the present invention can directly be used for handling and contain SO 2And do not contain H 2The various industrial waste gases of S contain SO 2Gas react to generate sulphur and reach and remove SO through directly entering the hydrogenation reduction device after the preheating 2And the purpose that reaches the environment protection emission requirement.
The SO that the present invention introduces 2The selective reduction catalyst carrier mainly contains TiO 2Or Al 2O 3Or ZrO 2Or SiO 2Perhaps wherein said two devices or many persons' mixture is formed.And add the surface acid alkalescence that one or more alkali metal or alkaline earth oxide are regulated carrier, add in I B, IIB in the periodic table of elements, IIIB, VB, VIB, VIIB, VIII, the VA family element one or more simultaneously and increase the activity stability of carrier.
The selective reduction catalyst carrier that the present invention introduces and uses can add corresponding assistant formation additive by technology moulding such as traditional extrusion, spin, compressing tablets in the forming process.Carrier that obtains and catalyst can make different shapes such as various bar shapeds, sphere, column, sheet type.The granularity of ball type carrier and catalyst is 2～10mm, and the granularity of bar shaped carrier and catalyst is φ (1-6) * (1-30) mm.
The active constituent of the selective reduction catalyst of introduction of the present invention mainly is CoO/MoO 3/ NiO/WO 3One or more, add decentralization that in I B in the periodic table of elements, II B, IIIB, VB, VIB, VIIB, VIII, the VA family element one or more increase activity of such catalysts stability and improve active constituent simultaneously.
The selective reduction catalyst of introduction of the present invention can adopt traditional dip loading mode, need to add complexing agents such as ammoniacal liquor, ethylenediamine, ammonium citrate, EDTA in the dipping process, make the preceding active constituent of dipping form complex compound, increase the dispersion of nano-particles degree and the uniformity on the catalyst.
Catalyst of the present invention also can adopt traditional kneading and compacting mode, will contain TiO 2/ SiO 2/ Al 2O 3/ ZrO 2Predecessor one or more and contain CoO/MoO 3/ NiO/WO 3One or more and the periodic table of elements of predecessor in one or more kneading and compactings simultaneously of predecessor in I B, IIB, IIIB, VB, VIB, VIIB, VIII, the VA family element.
Catalyst after the moulding must at room temperature be placed 0～48 hour, also can place under steam ambient 0～48 hour.Dried 0～24 hour under 100～150 ℃ of conditions then, roasting obtained finished catalyst in 4～8 hours under 400～600 ℃ of conditions.
The specific area of finished catalyst is 100～400m 2/ g, pore volume are that the average crushing strength of 0.2～0.6ml/g. is 100～300N/.
The main flow process of selective reduction sulphur recovery technology of introduction of the present invention comprises sour gas combustion furnace, waste heat boiler, first catalytic reactor, second catalytic reactor, SO 2Selective reduction reactor and remaining H 2S absorption tower and regenerator etc.The hot mode again of first catalytic reactor wherein, second catalytic reactor and tail gas hydrogenation reactor inlet can be selected variety of ways such as online heating furnace, heat exchanger, hot fusion.The inlet temperature of first, second catalytic reactor is 200～300 ℃, and the inlet temperature of tail gas hydrogenation reduction reactor is 160～300 ℃.The outlet of tail gas hydrogenation reduction reactor does not contain SO 2, COS/CS 2, only contain elemental sulfur and H 2Two kinds of sulfide of S.By behind condenser and the sulphur that the trap branch goes, enter in the air-flow of tail gas absorber and do not contain SO 2And elemental sulfur.Technology of the present invention also can adopt one or more converters, and this can determine according to the actual conditions of owner and sour gas.
Technology of the present invention also is applicable to handles H 2S concentration also can not used combustion furnace less than 20% low concentration sour gas, adopts the direct oxidation reactor to replace combustion furnace to operate, and the operating temperature of direct oxidation reactor can be controlled at below 600 ℃.Subsequent technique is basic identical.
Technology of the present invention can directly be used for handling and contain SO 2And do not contain H 2The various industrial waste gases of S contain SO 2Gas react to generate sulphur and reach and remove SO through directly entering the hydrogenation reduction device after the preheating 2And the purpose that reaches the environment protection emission requirement.
To technical scheme of the present invention, the applicant is summarized as follows:
A kind of selective reduction catalyst used for recovering sulfur, being included in and adopting selective reduction catalyst in the hydrogenation reduction device is elemental sulfur with the sulfurous gas selective reduction, it is characterized in that,
Described catalyst activity composition comprises CoO, MoO 3, NiO, WO 3In one or any several mixtures;
Described catalyst comprises carrier, and described carrier is TiO 2, Al 2O 3, ZrO 2Or SiO 2In a kind of or any several mixture;
On affiliated carrier, add the surface acid alkalescence that one or more alkali metal or alkaline earth oxide are regulated carrier;
One or more in I B, II B, IIIB, VB, VIB, VIIB, VIII, the VA family element increase the activity stability of carrier in the interpolation periodic table of elements on affiliated carrier.
Described catalyst adopts a kind of preparation in extrusion method, rolling ball method, the infusion process, the Preparation of catalysts process comprise the catalyst room temperature transfer put, drying and roasting;
Described catalyst was at room temperature placed 0～48 hour or was placed 12～24 hours;
Described drying condition is: baking temperature is 50～200 ℃ or 100～150 ℃, and be 1～48 hour or 12～24 hours drying time;
Described roasting condition is: sintering temperature is 200～600 ℃ or 300～500 ℃, roasting time be 1～24 hour or.2～12 hours.
The application of described catalyst in the selective reduction sulphur recovery is characterized in that, adopting catalyst of the present invention in the hydrogenation reduction device is elemental sulfur with the sulfurous gas selective reduction, contains SO in the described sulfurous gas 2
Also comprise H in the described sulfurous gas 2S, CS 2, the one or any several mixture among the COS.
The temperature of described reduction reaction is 100～400 ℃ or 160～300 ℃.
Total sulfur recovery is greater than 99.8%, SO in the flue gas 2Discharge capacity is less than 960mg/m 3
Compared with prior art, beneficial effect of the present invention is:
1) adopt the selective reduction catalyst of special exploitation with SO 2Be reduced to S, solved the shortcoming that traditional tail gas hydrogenation reactor does not generate sulphur, improved the total sulphur recovery efficiency of one way of device.
2) adopt special selective reduction catalyst, the operating temperature of hydrogenation reduction device is lower, and the practical operation temperature is 160～400 ℃.The hydrogenation reactor inlet temperature can be controlled at 160～200 ℃.Therefore only need just can reach the requirement of reactor inlet temperature by heat exchange fully, not need to re-use heating furnace, save the energy greatly.
3) since selectivity tail gas hydrogenation reactor only to SO 2Carry out hydrogenation reaction, can reduce 30%H at least 2Consumption.
4) because the SO2 in the tail gas is converted into S and collects in the molten sulfur storage tank in the hydrogenation reduction device, therefore, the load of tail gas absorber can reduce more than 30%.The steam consumption of corresponding regenerator can reduce by 30% at least.
5) because tail gas absorber and regenerator load reduce, response can reduce the volume of absorption tower and regenerator, reduces manufacturing cost.
6) owing to the gas flow temperature of coming out from trap has only 120～160 ℃, thus, no longer need cooler, air-flow can directly enter quench tower, has reduced equipment investment.
7) because the one way total sulfur recovery improves, be equivalent to reduce the operational load of package unit.
Description of drawings
Fig. 1 is a process flow diagram of the present invention.
Among the figure, 1-combustion furnace, 2-one-level reheater, 3-secondary reheater, three grades of reheaters of 4-, 5-first-stage condenser, 6-secondary condenser, three grades of condensers of 7-, 8-level Four condenser, 9-one-level converter, 10-secondary converter, 11-selective hydrogenation reduction reactor, 12-quench tower, the 13-absorption tower, 14-regenerator, 15-tail gas burning furnace, 16-Molten sulphur storage tank, 17-amine liquid storage tank, 18-blow-down stack.
The specific embodiment
Embodiment 1
Gained suspension washing will be deposited in and carry out press filtration on the filter press to clarification behind the titanium tetrachloride hydrolysis, gained solid in 110 ℃ of converters dry 24 hours, and it is amorphous TiO that the gained powder is measured its structure through the χ optical diffraction analysis 2, 1100 ℃ are burnt mistake is 18%.66% above-mentioned powder is added 32% water and 2% carboxymethyl cellulose fully mix the back and mediated 30 minutes on kneader, by 4mm orifice plate extrusion, 110 ℃ of dryings are 8 hours then on banded extruder, and 450 ℃ of roastings obtained carrier 1 in 4 hours.The specific area of gained strip carrier is 135m 2/ g, pore volume are 0.32ml/g.
The preparation of maceration extract: 29g ammonium heptamolybdate and 28g cobalt nitrate are dissolved in the mixed solution that 25% ammoniacal liquor and 1.4ml ethylenediamine form, obtain 150ml maceration extract 1.
Adopt the repeatedly mode of dipping, with the above-mentioned carrier 1 of this maceration extract 150ml dipping 180g, flood and discard raffinate after finishing, air dry is 24 hours under the room temperature, and 110 ℃ of dryings are 24 hours then, and 500 ℃ of roastings obtained catalyst sample A in 4 hours.
Embodiment 2
With concentration 15% Ti (SO 4) 2Solution adds 20% NaOH solution and carries out neutralization precipitation, with deionized water with washing of precipitate to there not being SO 4 2-, adopt the filter press press filtration to obtain filter cake, gained solid filter cake 110 ℃ of dryings 24 hours in baking oven adopt pulverizer to be crushed to the powder of granularity more than 300 orders.It is amorphous TiO that the gained powder is measured its structure through the χ optical diffraction analysis 2, 1100 ℃ are burnt mistake is 24%.
64% above-mentioned powder is added 34% water and 2% carboxymethyl cellulose fully mix the back and mediated 30 minutes on kneader, by 4mm orifice plate extrusion, 110 ℃ of dryings are 8 hours then on banded extruder, and 450 ℃ of roastings obtained carrier 2 in 4 hours.The specific area of gained strip carrier 2 is 145m2/g, and pore volume is 0.34ml/g.
Adopt the repeatedly mode of dipping, adopt the identical above-mentioned carrier 2 of maceration extract 150ml dipping 180g of embodiment 1, discard raffinate after dipping is finished, air dry is 24 hours under the room temperature, and 110 ℃ of dryings are 24 hours then, and 500 ℃ of roastings obtained catalyst sample B in 4 hours.
Embodiment 3
Adopt CO 2The saturated sodium aluminate solution that neutralizes, gained Al (OH) 3Washed back 120 ℃ of dryings after filtration 24 hours, and so can be crushed to greater than 300 order aluminium hydroxide dry powder.Get this dry powder 10kg, add carboxymethyl cellulose 0.2kg, nitric acid 0.32kg, deionized water 8kg mediated 1 hour, adopted Φ 3mm orifice plate extruded moulding, roasting in 550 ℃ then * 4 hours, the catalyst carrier 3 that obtains.The physical and chemical performance index of carrier 3 is specific area 395m2/g, pore volume 0.8ml/g, average crushing strength 255 newton/cm.
With the maceration extract 1 dipping 180g carrier 3 of 150ml embodiment 1, dipping discards raffinate after fully, and air dry is 24 hours under the room temperature, and 110 ℃ of dryings are 24 hours then, and 500 ℃ of roastings obtained catalyst sample C in 4 hours.
Embodiment 4
29g ammonium heptamolybdate and 28g cobalt nitrate are dissolved in 25% ammoniacal liquor and 1.4ml ethylenediamine, 0.3ml phosphoric acid H 3PO 4In the mixed solution of forming, obtain 150ml maceration extract 2, the pH value of guaranteeing gained solution is between 8～10.With being dipped in wherein through the spherical active aluminum oxide carrier 3 of the 180g of 120 ℃ of oven dry of external diameter φ 4～6mm, placed 12 hours the back that stirs, and then 120 ℃ of oven dry, 500 ℃ of roastings 3 hours promptly get catalyst sample D.Active aluminum oxide carrier 3 is the activated aluminas that adopt aluminium hydroxide high temperature fast dewatering explained hereafter, and its physical and chemical performance index is as follows: specific area 325m 2/ g, pore volume 0.5ml/g, average crushing strength 155 newton/cm, the aluminium oxide crystalline phase is mainly the γ type, is the η type on a small quantity.
Embodiment 5
29g ammonium heptamolybdate, 18g ammonium tungstate, 10g nickel nitrate are dissolved in the mixed solution that 25% ammoniacal liquor and 5g oxalic acid, 0.2g phosphoric acid forms, obtain the 210g carrier 1 that this maceration extract of 180ml maceration extract 2. usefulness 2 dipping embodiment 1 obtain, discard raffinate after dipping is complete, air dry is 24 hours under the room temperature, 110 ℃ of dryings are 24 hours then, and 500 ℃ of roastings obtained catalyst sample E in 4 hours.
Embodiment 6
According to the 210g carrier 2 that the identical methods preparation 180ml maceration extracts 2 dipping embodiment 2 of embodiment 5 obtain, dipping discards raffinate after fully, and air dry is 24 hours under the room temperature, and 110 ℃ of dryings are 24 hours then, and 500 ℃ of roastings obtained catalyst sample F in 4 hours.
Embodiment 7
According to 210 carriers 3 that the identical methods preparation 180ml maceration extracts 2 dipping embodiment 3 of embodiment 5 obtain, dipping discards raffinate after fully, and air dry is 24 hours under the room temperature, and 110 ℃ of dryings are 24 hours then, and 500 ℃ of roastings obtained catalyst sample G in 4 hours.
Embodiment 8
Gained suspension washing will be deposited in and carry out press filtration on the filter press to clarification behind the titanium tetrachloride hydrolysis, gained solid in 110 ℃ of converters dry 24 hours, and it is amorphous TiO that the gained powder is measured its structure through the χ optical diffraction analysis 2, 1100 ℃ are burnt mistake is 18%.29g ammonium heptamolybdate and 28g cobalt nitrate be dissolved in add above-mentioned powder 125g and 4g carboxymethyl cellulose in the mixed solution that 25% ammoniacal liquor and 1.4ml ethylenediamine form and fully mix the back and on kneader, mediated 30 minutes, on banded extruder, pass through 4mm orifice plate extrusion, air dry 24 hours under the room temperature then, 110 ℃ of dryings 8 hours, 450 ℃ of roastings obtained catalyst sample H. in 4 hours
Embodiment 9
With concentration 15% Ti 2(SO 4) 2Solution adds 20% NaOH solution and carries out neutralization precipitation, with deionized water with washing of precipitate to there not being SO 4 2-, adopt the filter press press filtration to obtain filter cake, gained solid filter cake 110 ℃ of dryings 24 hours in baking oven adopt pulverizer to be crushed to the powder of granularity more than 300 orders.It is amorphous TiO that the gained powder is measured its structure through the χ optical diffraction analysis 2, 1100 ℃ are burnt mistake is 24%.
The above-mentioned powder of 200g is added 3g sesbania powder, adds 31g ammonium heptamolybdate and 28g cobalt nitrate then and be dissolved in the mixed solution that 25% ammoniacal liquor and 2.5g citric acid, 2.8gEDTA form, fully mixing the back mediated 30 minutes on kneader, on banded extruder, pass through 4mm orifice plate extrusion, 110 ℃ of dryings are 8 hours then, and 450 ℃ of roastings obtained catalyst sample I. in 4 hours
Embodiment 10
The TiO that adopts embodiment 1 to obtain 2Dry powder 100g, add the aluminium hydroxide dry powder 150g that embodiment 3 obtains, add carboxymethyl cellulose 5g, distilled water 78g, fully mix the back and adopt 3mm clover orifice plate extruded moulding, dried 24 hours for 120～150 ℃, 400 ℃ of roastings obtained carrier 4. in 12 hours, adopted the repeatedly mode of dipping, maceration extract 1 this carrier 4 of dipping 180g with embodiment 1 resultant 150ml, placed under the room temperature 24 hours, 120 ℃ of dryings 8 hours, 500 ℃ of roastings obtained catalyst sample J. in 4 hours
Embodiment 11
In airtight polytetrafluoroethylcontainer container, adopt 120gTiCl 4The active aluminum oxide carrier 1000g that dipping uses according to embodiment 4, then through after hydrolysis, the washing, 120 ℃ of dryings 8 hours, 450 ℃ of roastings obtained the TiO of carrier 5. these carriers in 4 hours 2Content is 5% (m/m), and specific area is 298m2/g, and pore volume is 0.4ml/g.Adopt the 150ml maceration extract 1 of 150ml embodiment 1 configuration to flood 200g carrier 5, placed 48 hours under the room temperature, 150 ℃ of dryings 8 hours, 500 ℃ of roastings obtained catalyst sample K. in 12 hours
Embodiment 12
The aluminium hydroxide dry powder 1000g that adopts embodiment 3 to obtain adds tetra isopropyl titanium Ti[OCH (CH 3) 2] 4100g, mediated 2 hours, 60 ℃ of dryings 8 hours, 120 ℃ of dryings 8 hours, 150 ℃ of dryings 8 hours, 500 roastings 6 hours, obtain 150ml maceration extract 2 these carriers 6 of dipping 200g that carrier 6. adopts embodiment 5 to obtain, room temperature was placed 24 hours, 150 ℃ of dryings 8 hours, and 500 ℃ of roastings obtained catalyst sample L. in 12 hours
Embodiment 13
Employing concentration is 15% Ti 2(SO 4) 2The 1000g catalyst carrier 3 that solution 500g dipping embodiment 4 uses, reach the dipping balance after, adopt the deionized water washing to there not being SO 4 2-Till (adopt 5%BaCl 2In washings, detect less than SO 4 2-Till).50 ℃ of dryings 8 hours, 100 ℃ of dryings 8 hours, 180 ℃ of dryings 12 hours, 400 ℃ of roastings obtained maceration extract 1 this carrier 7 of dipping 2000g that carrier 7. adopts 1000ml embodiment 1 to obtain in 12 hours.Room temperature was placed 24 hours, 110 ℃ of dryings 8 hours, and 550 ℃ of roastings obtained catalyst sample M in 12 hours.
Embodiment 14
Fill in the stainless steel tubular type reactor of internal diameter 5mm being crushed to 20～40 purpose catalyst sample 5ml, the quartz sand mixing preheating of catalyst top filling same particle sizes, reactor adopts Electric heating.Adopt H in day island proper Tianjin GC-14B gas chromatograph on-line analysis reactor inlet and the exit gas 2S, SO 2, CS 2Content, adopt the GDX-301 carrier to analyze sulfide, 120 ℃ of column temperatures adopt thermal conductivity detector (TCD), 150 ℃ of detector temperatures are done carrier gas with hydrogen, flow velocity 28ml/min behind the post.
With SO 2+ H 2=S+H 2O, SO 2+ 3H 2→ H 2S+2H 2O is the index reaction, investigates the hydrogenation activity of different catalysts, and inlet gas is formed: H 2S 1%, SO 21%, H 2O 30%, and all the other are N 2, the gas volume air speed is 5000h -1, reaction temperature is 160～300 ℃.Calculate the SO of catalyst according to following formula 2Conversion ratio:
η SO 2 = M 0 - M 1 M 0 × 100 %
M wherein 0, M 1Then representative enters the mouth and exit SO respectively 2Volumetric concentration.
Calculate the yield of the element S of catalyst according to following formula:
η s = 1 - M 1 + ( N 1 - N 0 ) M 0
N wherein 0, N 1Represent the H in reactor inlet and exit respectively 2The S volumetric concentration.M 0, M 1Then representative enters the mouth and exit SO respectively 2Volumetric concentration.
The activity contrast of table 1 different catalysts sample
Figure G2008102378137D0000111

Claims (7)

1. selective reduction catalyst used for recovering sulfur, being included in and adopting selective reduction catalyst in the hydrogenation reduction device is elemental sulfur with the sulfurous gas selective reduction, it is characterized in that,
Described catalyst activity composition comprises CoO, MoO 3, NiO, WO 3In one or any several mixtures;
Described catalyst comprises carrier, and described carrier is TiO 2, Al 2O 3, ZrO 2Or SiO 2In a kind of or any several mixture;
On affiliated carrier, add the surface acid alkalescence that one or more alkali metal or alkaline earth oxide are regulated carrier;
One or more in I B, II B, III B, V B, VI B, VII B, VIII, the VA family element increase the activity stability of carrier in the interpolation periodic table of elements on affiliated carrier.
2. the catalyst that selective reduction sulphur recovery according to claim 1 is used is characterized in that, described catalyst adopts a kind of preparation in extrusion method, rolling ball method, the infusion process.
3. the catalyst that selective reduction sulphur recovery according to claim 2 is used is characterized in that, the Preparation of catalysts process comprise the catalyst room temperature transfer put, drying and roasting;
Described catalyst was at room temperature placed 0～48 hour or was placed 12～24 hours;
Described drying condition is: baking temperature is 50～200 ℃ or 100～150 ℃, and be 1～48 hour or 12～24 hours drying time;
Described roasting condition is: sintering temperature is 200～600 ℃ or 300～500 ℃, roasting time be 1～24 hour or.2～12 hours.
4. the application of the described catalyst of claim 1 in the selective reduction sulphur recovery is characterized in that, adopting the catalyst of claim 1 in the hydrogenation reduction device is elemental sulfur with the sulfurous gas selective reduction, contains SO in the described sulfurous gas 2
5. the application of catalyst according to claim 4 in the selective reduction sulphur recovery is characterized in that, also comprises H in the described sulfurous gas 2S, CS 2, the one or any several mixture among the COS.
6. the application of catalyst according to claim 4 in the selective reduction sulphur recovery is characterized in that, the temperature of described reduction reaction is 100～400 ℃ or 160～300 ℃.
7. the application of catalyst according to claim 6 in the selective reduction sulphur recovery is characterized in that, total sulfur recovery is greater than 99.8%, SO in the flue gas 2Discharge capacity is less than 960mg/m 3
CN200810237813A 2008-12-02 2008-12-02 Selective reduction catalyst used for recovering sulfur, preparation method and application thereof Pending CN101745399A (en)

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