CN107175108A - A kind of cobalt series catalyst that sulphur processed is reduced for sulfur dioxide in flue gas and its production and use - Google Patents

A kind of cobalt series catalyst that sulphur processed is reduced for sulfur dioxide in flue gas and its production and use Download PDF

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CN107175108A
CN107175108A CN201710558187.0A CN201710558187A CN107175108A CN 107175108 A CN107175108 A CN 107175108A CN 201710558187 A CN201710558187 A CN 201710558187A CN 107175108 A CN107175108 A CN 107175108A
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catalyst
carrier
load capacity
auxiliary agent
flue gas
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李春山
葛亭亭
左村村
陈洪楠
张锁江
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Institute of Process Engineering of CAS
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Institute of Process Engineering of CAS
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Priority to CN201710558187.0A priority Critical patent/CN107175108A/en
Priority to PCT/CN2017/101785 priority patent/WO2019010811A1/en
Publication of CN107175108A publication Critical patent/CN107175108A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/75—Cobalt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8603—Removing sulfur compounds
    • B01D53/8609—Sulfur oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/02—Preparation of sulfur; Purification
    • C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
    • C01B17/0404—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process
    • C01B17/0426—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process characterised by the catalytic conversion
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/02—Preparation of sulfur; Purification
    • C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
    • C01B17/0473—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by reaction of sulfur dioxide or sulfur trioxide containing gases with reducing agents other than hydrogen sulfide
    • C01B17/0491—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by reaction of sulfur dioxide or sulfur trioxide containing gases with reducing agents other than hydrogen sulfide with hydrogen or hydrogen-containing mixtures, e.g. synthesis gas
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

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Abstract

It is used for SO in flue gas the invention provides one kind2Co series catalysts of reduction sulphur processed and its production and use, the catalyst includes carrier and the active component being coated on carrier and auxiliary agent, wherein active component is Co oxide, and auxiliary agent is any one in Cu, Ni, La, Mg, Ca or Ba or at least two combination of oxides.The preparation method is：Active component and auxiliary agent are carried on carrier using equi-volume impregnating, through drying, roasting and vulcanization, Co series catalysts are made.Co series catalysts neutral component of the present invention is uniformly dispersed, performance stable and epigranular, is applicable in fixed bed reactors be catalyzed SO in flue gas2Reduction sulphur processed.

Description

A kind of cobalt series catalyst and its preparation side that sulphur processed is reduced for sulfur dioxide in flue gas Method and purposes
Technical field
The invention belongs to fume treatment field, it is related to a kind of for SO in flue gas2The Co series catalysts of reduction sulphur processed and its Processing method and purposes, more particularly to a kind of active component is uniformly dispersed, performance stable, mechanical strength is good and even-grained suitable For flue gas SO2Produce Co series catalysts of elemental sulfur and its production and use.
Background technology
Pyrometallurgy (pyrometallurgy) is to produce high temperature with fuel, electric energy or other energy, at high temperature, from ore deposit The process with refined metals or its compound is extracted in stone.Pyrometallurgy typically divides ore to prepare, smelts, refined and flue gas The steps such as processing, are most ancient and largest modern Application metal smelt methods.The element sulphur existed with simple substance sulfur speciation But turn into national economy production in occupation of the light status of lumping weight is lifted in the industry sulphur such as dyestuff, rubber, papermaking and military project Main raw materials for production, and because China's sulphur mineral reserve are deficient, be required for spending huge foreign exchange imported sulphur every year.In face of this The situation of sample we can not deny that harmful sulphur only is changed into beneficial sulphur (if for example by SO in flue gas2It is changed into available resource Sulphur) it just can thoroughly solve Utilizing question of the China in terms of Sulphur ressource.Therefore, the SO in flue gas2Selective is reduced to Elemental sulfur will be a kind of with broad mass market prospect, not only with economic benefit but also with social benefit, and be adapted to China's national situation Fume desulphurization method.
At present, many domestic and international experts and scholars have also been made that great efforts in terms of desulfurization basis and technical research, Think optimal processing high concentration SO2Method is by SO2Selective reduction is simple substance S.Sulfur dioxide flue gas sulphur technology is main There are 2 kinds of direct-reduction process and indirect reduction method.Direct-reduction process can be divided into H according to the difference of reducing agent used2Reducing process, Charcoal reduction method, hydro carbons (mainly CH4) reducing process, CO reducing process and NH3Reducing process.And other method is also due to a variety of causes, It is difficult to industrialization.Have been carried out it is industrialized have a hydrogen reduction method and high-temperature methane reducing process, but H2Source transport With store all inconvenient and poor operability, and the consumption of natural gas and oxygen is huge in high-temperature methane reducing process.
At present, traditional sulphur dioxide reduction method for preparing catalyst has sol-gel process and infusion process.Sol-gel Method is that active component is doped on colloid, together drying roasting, and active component is equal in catalytic inner distribution in this method One.For example, Rao Yuxiang et al. adulterates in perovskite preparation process, some Co, Mo and Ni etc. are baking mixed, the catalysis of preparation Agent is used for catalytic methane and reduces sulfur dioxide process, has obtained good effect, but catalytic temperature is higher in this method, process energy Consumption it is too big (" research of the perovskite type composite oxide catalyst to methane desulfurization ", space Xiang etc. of having mercy on,《Petrochemical industry》, 2004 Volume 33).
The sulphur dioxide reduction method for preparing catalyst or infusion process being most widely used, because impregnating method preparation technique Simply, and active component is higher in catalyst surface concentration, concentration is gradually reduced from outside to inside, meets technique and scale metaplasia Production is required.In infusion process, used carrier generally selects some basic anhydride or amphoteric oxide, it is therefore an objective to inhale sulfur dioxide Catalyst surface is attached to, promotes catalytic process.For example, the Moody of Los Alamos National Laboratories uses catalytic performance most Good Ru/A12O3Make catalyst to be studied, when reaction temperature is 156 DEG C, the conversion ratio of catalyst is more than 90%, substantially On there is no accessory substance H2S, but it is too high with noble metal cost.Boswell et al. was once supported on stone with Fe systems metal (Fe, Co, Ni) As the catalyst to investigating H on the porous class material such as cotton, diatomite and porous brick class2Reduce SO2Reaction.King's generation loyalty et al. It is oxide carried in A1 using rare earth metal (Nb, Ce, Pr, La, Sm)2O3On, SO is reduced to CO2Catalytic process is studied, hair Existing rare earth oxide has good desulfurized effect, Pr/A12O3It is best.In addition, CeO2It is also that reduction and desulfurization effect is preferably carried Body, Liu researchs show Ni/CeO2And Cu/CeO2The yield of elemental sulfur at 500 DEG C is more than 95%.Mulligan et al. is used Pure crystal MoS2, WS, FeS and support type MoS2/A12O3Carry out research and find that MoS is higher than the selectivity of WS and FeS catalyst, bear Load type MoS2/A12O3Compare A12O3Active selectable is higher, but the preparation method is considerably complicated, is unsuitable for large-scale production.
In a word, catalyst of the prior art, costly, some preparation methods are complicated, some work for some preparation costs Property it is poor, in view of economy and commercial Application angle consider, developing low-cost, preparation technology is simple, and the high catalysis of activity Agent is inevitable.
The content of the invention
For problems of the prior art, it is used for SO in flue gas the invention provides one kind2The Co systems of reduction sulphur processed Catalyst and its production and use.Metal oxide of the invention by the active component Co in supported on carriers, and lead to Its synergy with auxiliary agent is crossed, the catalyst can be made for SO2With higher activity during reduction sulphur processed, and compared with High selectivity；Also, the Co series catalysts neutral component is uniformly dispersed, performance stable and epigranular, is applicable to SO in flue gas is catalyzed in fixed bed reactors2Reduction sulphur processed.
For up to this purpose, the present invention uses following technical scheme：
An object of the present invention is to provide a kind of for SO in flue gas2The Co series catalysts of reduction sulphur processed, it is described to urge Agent includes carrier and the active component that is coated on carrier and auxiliary agent, and wherein active component is Co oxide, auxiliary agent be Cu, Any one in Ni, La, Mg, Ca or Ba or at least two combination of oxides.
Wherein, the auxiliary agent can Cu and Ni combination, La and Mg combination, Ca and Ba combination, Cu, Ni and La group Close, La, Mg and Ca combination, Mg, Ca and Ba combination, Cu, Ni, La, Mg and Ca combination etc..
Below as currently preferred technical scheme, but the limitation of the technical scheme provided not as the present invention, pass through Following technical scheme, can preferably reach and realize the technical purpose and beneficial effect of the present invention.
As currently preferred technical scheme, the carrier is γ-Al2O3, SiO2, TiO2Or any one in ZSM-5 Or at least two combination.
Preferably, the carrier is the homogeneous particle of shape, preferably spherical particle and/or powder.
In the present invention, the carrier is not limited in above-mentioned listed form, and other can reach the special form of effect same The homogeneous particle of shape may be applicable to the present invention.
As currently preferred technical scheme, in the catalyst in active component Co load capacity for 3wt%~ 16wt%, such as 3wt%, 5wt%, 7wt%, 10wt%, 13wt%, 15wt% or 16wt%, it is not limited to listed Other unrequited numerical value are equally applicable in the numerical value of act, the number range.
In the present invention, the load capacity of the Co needs to control within the specific limits, if Co load capacity is excessive, can make catalysis Agent specific surface area is reduced rapidly；If Co load capacity is too low, catalyst active center's concentration reduction can be made, and then influence catalyst Catalytic performance.
Preferably, in the catalyst in auxiliary agent Cu load capacity be 1wt%~6wt%, such as 1wt%, 2wt%, 3wt%, 4wt%, 5wt% or 6wt% etc., it is not limited to other are unrequited in cited numerical value, the number range Numerical value is equally applicable.
Preferably, in the catalyst in auxiliary agent Ni load capacity be 1wt%~6wt%, such as 1wt%, 2wt%, 3wt%, 4wt%, 5wt% or 6wt% etc., it is not limited to other are unrequited in cited numerical value, the number range Numerical value is equally applicable.
Preferably, in the catalyst in auxiliary agent La load capacity be 1wt%~6wt%, such as 1wt%, 2wt%, 3wt%, 4wt%, 5wt% or 6wt% etc., it is not limited to other are unrequited in cited numerical value, the number range Numerical value is equally applicable.
Preferably, in the catalyst in auxiliary agent Mg load capacity 1wt%~6wt%, such as 1wt%, 2wt%, 3wt%, 4wt%, 5wt% or 6wt% etc., it is not limited to other are unrequited in cited numerical value, the number range Numerical value is equally applicable.
Preferably, in the catalyst in auxiliary agent Ca load capacity 1wt%~6wt%, such as 1wt%, 2wt%, 3wt%, 4wt%, 5wt% or 6wt% etc., it is not limited to other are unrequited in cited numerical value, the number range Numerical value is equally applicable.
Preferably, in the catalyst in auxiliary agent Ba load capacity be 1wt%~6wt%, such as 1wt%, 2wt%, 3wt%, 4wt%, 5wt% or 6wt% etc., it is not limited to other are unrequited in cited numerical value, the number range Numerical value is equally applicable.
The second object of the present invention is to provide a kind of preparation method of above-mentioned Co series catalysts, and the preparation method is： Active component and auxiliary agent are carried on carrier using equi-volume impregnating, through drying, roasting and vulcanization, the catalysis of Co systems is made Agent.
As currently preferred technical scheme, the preparation method specifically includes following steps：
(1) cobalt source and promoter metal salt are mixed and made into solution；
(2) carrier is added into step (1) described solution, incipient impregnation, the carrier after being impregnated is carried out；
(3) carrier after step (2) described dipping is dried and is calcined, and obtains catalyst precursor；
(4) step (3) described catalyst precursor is vulcanized, obtains Co series catalysts.
In the present invention, by vulcanizing to catalyst precursor, the activity and resistant to sulfur of catalyst can be increased substantially Property.
As currently preferred technical scheme, step (1) described cobalt source is cobalt nitrate.
Preferably, step (1) the promoter metal salt is nickel nitrate, copper nitrate, lanthanum nitrate, magnesium nitrate, calcium nitrate or nitre Any one in sour barium or at least two combination, the combination is typical but non-limiting examples have：Nickel nitrate and copper nitrate Combination, the combination of lanthanum nitrate and magnesium nitrate, the combination of calcium nitrate and barium nitrate, nickel nitrate, copper nitrate, lanthanum nitrate and magnesium nitrate Combination, lanthanum nitrate, magnesium nitrate, combination of calcium nitrate and barium nitrate etc..
Preferably, the consumption of step (1) described cobalt source is：Make the load capacity of Co in active component in the catalyst after load For 3wt%~16wt%, such as 3wt%, 5wt%, 7wt%, 10wt%, 13wt%, 15wt% or 16wt%, but simultaneously not only It is limited to other unrequited numerical value in cited numerical value, the number range equally applicable.
Preferably, the consumption of promoter metal salt is in step (1) described solution：Make the load of Cu in the catalyst after load Measure as 1%~6wt%, such as 1wt%, 2wt%, 3wt%, 4wt%, 5wt% or 6wt%, it is not limited to cited Numerical value, other unrequited numerical value are equally applicable in the number range；Ni load capacity be 1%~6wt%, such as 1wt%, 2wt%, 3wt%, 4wt%, 5wt% or 6wt% etc., it is not limited to cited numerical value, in the number range, other are not The numerical value enumerated is equally applicable；La load capacity be 1%~6wt%, such as 1wt%, 2wt%, 3wt%, 4wt%, 5wt% or 6wt% etc., it is not limited to other unrequited numerical value are equally applicable in cited numerical value, the number range；Mg's is negative 1%~6wt% of carrying capacity, such as 1wt%, 2wt%, 3wt%, 4wt%, 5wt% or 6wt%, it is not limited to cited Numerical value, other unrequited numerical value are equally applicable in the number range；Ca 1%~6wt% of load capacity, such as 1wt%, 2wt%, 3wt%, 4wt%, 5wt% or 6wt% etc., it is not limited to cited numerical value, in the number range, other are not The numerical value enumerated is equally applicable；Ba load capacity be 1%~6wt%, such as 1wt%, 2wt%, 3wt%, 4wt%, 5wt% or 6wt% etc., it is not limited to other unrequited numerical value are equally applicable in cited numerical value, the number range.
Herein, it is not that the auxiliary agent limited after load includes Cu, Ni, La, Mg, Ca and Ba, but can wherein appoint Meaning one kind or at least two, as long as the concentration after load meets above range.
Preferably, solvent is water in step (1) described solution.
As currently preferred technical scheme, step (2) described carrier is γ-Al2O3, SiO2, TiO2Or in ZSM-5 Any one or at least two combination.
Preferably, the time of step (2) described incipient impregnation is 1h~6h, such as 1h, 2h, 3h, 4h, 5h or 6h, It is not limited to other unrequited numerical value are equally applicable in cited numerical value, the number range.
Preferably, step (3) described drying temperature be 100 DEG C~130 DEG C, such as 100 DEG C, 105 DEG C, 110 DEG C, 115 DEG C, 120 DEG C, 125 DEG C or 130 DEG C etc., it is not limited to other unrequited numerical value are same in cited numerical value, the number range Sample is applicable.
Preferably, step (3) drying time is 1h~6h, such as 1h, 2h, 3h, 4h, 5h or 6h, but simultaneously not only It is limited to other unrequited numerical value in cited numerical value, the number range equally applicable.
Preferably, the temperature of step (3) described roasting be 400 DEG C~600 DEG C, such as 400 DEG C, 430 DEG C, 450 DEG C, 470 DEG C, 500 DEG C, 530 DEG C, 550 DEG C, 570 DEG C or 600 DEG C etc., it is not limited in cited numerical value, the number range other Unrequited numerical value is equally applicable.
Preferably, the time of step (3) described roasting is 6h~12h, such as 6h, 8h, 10h or 12h, but is simultaneously not only limited It is equally applicable in other unrequited numerical value in cited numerical value, the number range.
Preferably, step (3) roasting is carried out in Muffle furnace.
As currently preferred technical scheme, step (4) vulcanization is in H2S and H2Mixed atmosphere under carry out.
Preferably, the H2S and H2Mixed atmosphere in H2S volume content be 5%~15%, such as 5%, 7%, 10%th, 13% or 15% etc., it is not limited to other unrequited numerical value are equally fitted in cited numerical value, the number range With.
Preferably, the temperature of step (4) described vulcanization be 400 DEG C~600 DEG C, such as 400 DEG C, 430 DEG C, 450 DEG C, 470 DEG C, 500 DEG C, 530 DEG C, 550 DEG C, 570 DEG C or 600 DEG C etc., it is not limited in cited numerical value, the number range other Unrequited numerical value is equally applicable.
Preferably, the time of step (4) described vulcanization is 0.5h~6h, such as 0.5h, 1h, 2h, 3h, 4h, 5h or 6h, It is not limited to other unrequited numerical value are equally applicable in cited numerical value, the number range.
Preferably, step (4) vulcanization is carried out in tube furnace.
The third object of the present invention is the provision of the purposes of above-mentioned Co series catalysts, will the Co series catalysts be used for SO in flue gas is catalyzed in fixed bed reactors2Reduction prepares elemental sulfur.
Preferably, SO in the flue gas2Content for 20%~30%, such as 20%, 22%, 24%, 26%, 28% or 30% etc., it is not limited to other unrequited numerical value are equally applicable in cited numerical value, the number range.
As currently preferred technical scheme, SO in the catalysis flue gas2The method that reduction prepares elemental sulfur is：
The Co series catalysts are loaded in fixed bed reactors, in discharge system after air, flue gas and coal gas are through pre- Heat is entered back into fixed bed reactors and reacted at 350 DEG C~450 DEG C, by the SO in flue gas to 300 DEG C~450 DEG C2Also Original prepares elemental sulfur.
Catalyst after will vulcanizing, samples and is screened out after broken the catalyst granules of reasonable particle diameter, be put into fixed bed Effect assessment is carried out on micro anti-evaluation device, by sulphur crystallization and dewater treatment, tail gas is analyzed, conversion ratio is calculated And selectivity.
Compared with prior art, the invention has the advantages that：
The present invention cooperates with work with auxiliary agent by the metal oxide of the active component Co in supported on carriers, and by it With the catalyst can be made for SO2With higher activity, and higher selectivity during reduction sulphur processed；Also, institute State that Co series catalysts neutral components are uniformly dispersed, performance is stable and epigranular, be applicable to be catalyzed in fixed bed reactors SO in flue gas2Reduction sulphur processed, makes SO2Conversion ratio up to more than 90%, selectivity is up to more than 90%.
Meanwhile, catalyst of the present invention can carry out regeneration treatment after the deactivation, it is only necessary to which in-site secondary is calcined and vulcanized, Catalyst activity can both recover, and improve resource recycling rate.
Brief description of the drawings
Fig. 1 is the effect evaluating device schematic diagram of Co series catalysts of the present invention；
Wherein, 1- preheaters, 2- fixed bed reactors, 3- sulphur crystallizing tank, 4- remove water pot, 5- drying tubes, the inspection of 6- tail gas Survey, 7- tail gas clean-ups.
Embodiment
For the present invention is better described, technical scheme is readily appreciated, below to the present invention further specifically It is bright.But following embodiments is only the simple example of the present invention, the scope of the present invention is not represented or limits, this Invention protection domain is defined by claims.
Specific embodiment of the invention part provides a kind of for SO in flue gas2The Co series catalysts and its system of reduction sulphur processed Preparation Method, the catalyst includes carrier and the active component being coated on carrier and auxiliary agent, and wherein active component is Co oxygen Compound, auxiliary agent is any one in Cu, Ni, La, Mg, Ca or Ba or at least two combination of oxides.
Its preparation method is：Active component and auxiliary agent are carried on carrier using equi-volume impregnating, through drying, roasting And vulcanization, Co series catalysts are made.
Catalytic effect evaluation is carried out to the Co series catalysts, its device is as shown in figure 1, the Co series catalysts are loaded into In fixed bed reactors 2, first with the air in nitrogen exclusion system, then the temperature of preheater 1 risen into 300~450 DEG C, fixed bed Reactor 2 is warming up to 350~450 DEG C, after temperature stabilization, and flue gas (reacting gas) is passed through in proportion and coal gas (goes back Primordial Qi Body), after fixed bed reactors 2, sulphur crystallizing tank 3 and except water pot 4, quantitative analysis is carried out to tail gas, SO is calculated2Conversion ratio And selectivity.
It is below present invention typical case but non-limiting example：
Embodiment 1：
Present embodiments provide a kind of for SO in flue gas2Co series catalysts of reduction sulphur processed and preparation method thereof, it is described Method comprises the following steps：
(1) γ-Al of 15g fixation mesh number are weighed2O3Particle, is put into small beaker, progressively instills deionized water, works as water Just it is sufficiently impregnated γ-Al2O3When stop drip, weigh calculate add water amount, determine 15g carrier γ-Al2O3Water suction 15.3g；
(2) preparation 14wt%Co/ γ-Al are calculated by carrier quality2O3Co needed for catalyst (carrier is 15g) (NO3)2·6H2O amount, wherein 14% is the quality of metal oxide and the ratio of carrier quality.By 8.16g Co (NO3)2· 6H2O's is dissolved in 15.3mL deionized water, and stirring is made into the Co (NO of required concentration to being completely dissolved3)2Solution；Then should Solution once pours into the γ-Al for having weighed up 15g2O3In the small beaker of carrier, and it is stirred continuously, carrier is put just by thorough impregnation Set to 0 .5h.
(3) above-mentioned catalyst is put into 110 DEG C of baking oven and dries 6h, be then placed in Muffle furnace with temperature programming extremely 500 DEG C of roasting 12h, the oxide that Co is obtained after cooling is equally distributed in γ-Al2O3Catalyst precarsor；
(4) catalyst precarsor is put into tube furnace, in 10%H2S/H2Presulfurization 1h at 400 DEG C of atmosphere, then drops to room Temperature, produces uniform particle sizes, the uniform 14%Co/ γ-Al of Active components distribution2O3Catalyst.
Precise 1g catalyst, is put into micro anti-evaluation device and is evaluated, after tail gas is tested, calculating is obtained SO2Conversion ratio is 93.2%, and selectivity is 90.5%.
Embodiment 2：
Present embodiments provide a kind of for SO in flue gas2Co series catalysts of reduction sulphur processed and preparation method thereof, it is described Method comprises the following steps：
(1) γ-Al of 15g fixation mesh number are weighed2O3Particle, is put into small beaker, progressively instills deionized water, works as water Just it is sufficiently impregnated γ-Al2O3When stop drip, weigh calculate add water amount, determine 15g carrier γ-Al2O3Water suction 15.3g；
(2) preparation 14%Co-4%Cu/ γ-Al are calculated by carrier quality2O3Co needed for catalyst (carrier is 15g) (NO3)2·6H2O and Cu (NO3)2·3H2O amount.By 8.16g Co (NO3)2·6H2O and 1.82g Cu (NO3)2·3H2O's It is dissolved in 15.3mL deionized water, stirring is made into the dipping solution of required concentration to being completely dissolved；Then by the solution once Pour into and weighed up 15g γ-Al2O3In the small beaker of carrier, and it is stirred continuously, carrier places 0.5h just by thorough impregnation.
(3) above-mentioned catalyst is put into 110 DEG C of baking oven and dries 6h, be then placed in Muffle furnace with temperature programming extremely 500 DEG C of roasting 12h, the oxide that Co and Cu is obtained after cooling is equally distributed in γ-Al2O3Catalyst precarsor；
(4) catalyst precarsor is put into tube furnace, in 10%H2S/H2Presulfurization 1h at 400 DEG C of atmosphere, then drops to room Temperature, produces uniform particle sizes, the uniform 14%Co-4%Cu/ γ-Al of Active components distribution2O3Catalyst.
Precise 1g catalyst, is put into micro anti-evaluation device and is evaluated, after tail gas is tested, calculating is obtained SO2Conversion ratio is 94.0%, and selectivity is 96.1%.
Embodiment 3：
Present embodiments provide a kind of for SO in flue gas2Co series catalysts of reduction sulphur processed and preparation method thereof, it is described Method comprises the following steps：
(1) γ-Al of 15g fixation mesh number are weighed2O3Particle, is put into small beaker, progressively instills deionized water, works as water Just it is sufficiently impregnated γ-Al2O3When stop drip, weigh calculate add water amount, determine 15g carrier γ-Al2O3Water suction 15.3g；
(2) preparation 14%Co-4%Cu-2%La/ γ-Al are calculated by carrier quality2O3Catalyst (carrier is 15g) institute Need Co (NO3)2·6H2O、Cu(NO3)2·3H2O and La (NO3)3·6H2O amount.By 8.16g Co (NO3)2·6H2O、1.82g Cu (NO3)2·3H2O and 0.9352g La (NO3)3·6H2O's is dissolved in 15.3mL deionized water, stirs to completely molten The dipping solution of concentration needed for solution is made into.Then the solution is once poured into and has weighed up 15g γ-Al2O3In the small beaker of carrier, And be stirred continuously, carrier places 0.5h just by thorough impregnation；
(3) above-mentioned catalyst is put into 100 DEG C of baking oven and dries 5h, be then placed in Muffle furnace with temperature programming extremely 450 DEG C of roasting 10h, the oxide that Co, Cu and La are obtained after cooling is equally distributed in γ-Al2O3Catalyst precarsor；
(4) catalyst precarsor is put into tube furnace, in 10%H2S/H2Presulfurization 4h at 500 DEG C of atmosphere, then drops to room Temperature, produces uniform particle sizes, the uniform 14%Co-4%Cu-2%La/ γ-Al of Active components distribution2O3Catalyst.
Precise 1g catalyst, is put into micro anti-evaluation device and is evaluated, after tail gas is tested, calculating is obtained SO2Conversion ratio is 93.8%, and selectivity is 96.5%.
Embodiment 4：
Present embodiments provide a kind of for SO in flue gas2Co series catalysts of reduction sulphur processed and preparation method thereof, it is described Method comprises the following steps：
(1) γ-Al of 15g fixation mesh number are weighed2O3Particle, is put into small beaker, progressively instills deionized water, works as water Just it is sufficiently impregnated γ-Al2O3When stop drip, weigh calculate add water amount, determine 15g carrier γ-Al2O3Water suction 15.3g；
(2) preparation 14%Co-4%Cu/ γ-Al are calculated by carrier quality2O3Co needed for catalyst (carrier is 15g) (NO3)2·6H2O and Cu (NO3)2·3H2O amount.By 8.16g Co (NO3)2·6H2O and 1.82g Cu (NO3)2·3H2O's It is dissolved in 15.3mL deionized water, stirring is made into the dipping solution of required concentration to being completely dissolved.Then by the solution once Pour into and weighed up 15g γ-Al2O3In the small beaker of carrier, and it is stirred continuously, carrier places 0.5h just by thorough impregnation；
(3) above-mentioned catalyst is put into 130 DEG C of baking oven and dries 2h, be then placed in Muffle furnace with temperature programming extremely 550 DEG C of roasting 7h, the oxide that Co and Cu is obtained after cooling is equally distributed in γ-Al2O3Catalyst precarsor；
(4) catalyst precarsor is put into tube furnace, in 10%H2S/H2Presulfurization 2h at 600 DEG C of atmosphere, then drops to room Temperature, produces uniform particle sizes, the uniform 14%Co-4%Cu/ γ-Al of Active components distribution2O3Catalyst.
Precise 1g catalyst, is put into micro anti-evaluation device and is evaluated, after tail gas is tested, calculating is obtained SO2Conversion ratio is 86.5%, and selectivity is 93.4%.
Embodiment 5：
Present embodiments provide a kind of for SO in flue gas2Co series catalysts of reduction sulphur processed and preparation method thereof, it is described Method comprises the following steps：
(1) γ-Al of 15g fixation mesh number are weighed2O3Particle, is put into small beaker, progressively instills deionized water, works as water Just it is sufficiently impregnated γ-Al2O3When stop drip, weigh calculate add water amount, determine 15g carrier γ-Al2O3Water suction 15.3g；
(2) preparation 14%Co-6%Cu/ γ-Al are calculated by carrier quality2O3Co needed for catalyst (carrier is 15g) (NO3)2·6H2O and Cu (NO3)2·3H2O amount.By 8.16g Co (NO3)2·6H2O and 2.73g Cu (NO3)2·3H2O's It is dissolved in 15.3mL deionized water, stirring is made into the dipping solution of required concentration to being completely dissolved.Then by the solution once Pour into and weighed up 15g γ-Al2O3In the small beaker of carrier, and it is stirred continuously, carrier places 0.5h just by thorough impregnation；
(3) above-mentioned catalyst is put into 110 DEG C of baking oven and dries 6h, be then placed in Muffle furnace with temperature programming extremely 500 DEG C of roasting 12h, the oxide that Co and Cu is obtained after cooling is equally distributed in γ-Al2O3Catalyst precarsor；
(4) catalyst precarsor is put into tube furnace, in 10%H2S/H2Presulfurization 1h at 400 DEG C of atmosphere, then drops to room Temperature, produces uniform particle sizes, the uniform 14%Co-6%Cu/ γ-Al of Active components distribution2O3Catalyst.
Precise 1g catalyst, is put into micro anti-evaluation device and is evaluated, after tail gas is tested, calculating is obtained SO2Conversion ratio is 92.5%, and selectivity is 94.3%.
Embodiment 6：
Present embodiments provide a kind of for SO in flue gas2Co series catalysts of reduction sulphur processed and preparation method thereof, it is described Method comprises the following steps：
(1) SiO of 15g fixation mesh number is weighed2Particle, is put into small beaker, progressively instills deionized water, when water just It is sufficiently impregnated SiO2When stop drip, weigh calculate add water amount, determine 15g carrier S iO2Absorb water 16.5g；
(2) preparation 14%Co/SiO is calculated by carrier quality2Co (NO needed for catalyst (carrier is 15g)3)2·6H2O Amount.By 8.16g Co (NO3)2·6H2O is dissolved in 16.5mL deionized water, and stirring is made into required concentration to being completely dissolved Dipping solution.Then the solution is once poured into and has weighed up 15gSiO2In the small beaker of carrier, and it is stirred continuously, carrier is just Well by thorough impregnation, 0.5h is placed；
(3) above-mentioned catalyst is put into 110 DEG C of baking oven and dries 6h, be then placed in Muffle furnace with temperature programming extremely 500 DEG C of roasting 12h, the oxide that Co is obtained after cooling is equally distributed in SiO2Catalyst precarsor；
(4) catalyst precarsor is put into tube furnace, in 10%H2S/H2Presulfurization 1h at 400 DEG C of atmosphere, then drops to room Temperature, produces uniform particle sizes, the uniform 14%Co/SiO of Active components distribution2Catalyst.
Precise 1g catalyst, is put into micro anti-evaluation device and is evaluated, after tail gas is tested, calculating is obtained SO2Conversion ratio is 60.4%, and selectivity is 74.6%.
Embodiment 7：
Present embodiments provide a kind of for SO in flue gas2Co series catalysts of reduction sulphur processed and preparation method thereof, it is described Method comprises the following steps：
(1) γ-Al of 15g fixation mesh number are weighed2O3Particle, is put into small beaker, progressively instills deionized water, works as water Just it is sufficiently impregnated γ-Al2O3When stop drip, weigh calculate add water amount, determine 15g carrier γ-Al2O3Water suction 15.3g；
(2) preparation 14%Co+4%Cu+4%Ni/ γ-Al are calculated by carrier quality2O3Catalyst (carrier is 15g) is urged Co (NO needed for agent (carrier is 15g)3)2·6H2O, Cu (NO3)2·3H2O and Ni (NO3)2·6H2O, amount.By 8.16g's Co(NO3)2·6H2O, 1.82g Cu (NO3)2·3H2O and 2.34g Ni (NO3)2·6H2O is dissolved in 15.3mL deionized water In, stirring is made into the mixed solution of required concentration to being completely dissolved.Then the solution is once poured into and has weighed up 15g γ-Al2O3 In the small beaker of carrier, and it is stirred continuously, carrier places 0.5h just by thorough impregnation；
(3) above-mentioned catalyst is put into 110 DEG C of baking oven and dries 6h, be then placed in Muffle furnace with temperature programming extremely 500 DEG C of roasting 12h, the oxide that Co, Cu and Ni are obtained after cooling is equally distributed in γ-Al2O3Catalyst precarsor；
(4) catalyst precarsor is put into tube furnace, in 10%H2S/H2Presulfurization 1h at 400 DEG C of atmosphere, then drops to room Temperature, produces uniform particle sizes, the uniform 14%Co+4%Cu+4%Ni/ γ-Al of Active components distribution2O3Catalyst.
Precise 1g catalyst, is put into micro anti-evaluation device and is evaluated, after tail gas is tested, calculating is obtained SO2Conversion ratio is 91.6%, and selectivity is 92.5%.
Embodiment 8：
A kind of evaluation method of the Co series catalysts is present embodiments provided, by the 14%Co-4%Cu-2% of presulfurization La/γ-Al2O3Catalyst precise 1g, is loaded into fixed bed reactors and is evaluated.400 DEG C of reaction temperature, reaction is empty Speed is 5000h-1, simulate SO in metallurgical gas2Ratio is 9.65%, CO and H in reduction bottle coal gas2Total amount be SO2Twice. Life-span is carried out to the component catalyst of Co systems three and regeneration is evaluated.After catalyst operation 100h, SO2Conversion ratio and sulphur selectivity Remain to reach 90%.Finally, regeneration treatment is carried out to the catalyst of inactivation, by carrying out original position two to catalyst in the reactor After secondary roasting and vulcanization, catalyst activity can recover.
From above-described embodiment as can be seen that the present invention is by the metal oxide of the active component Co in supported on carriers, And by its synergy with auxiliary agent, the catalyst can be made for SO2With higher activity during reduction sulphur processed, with And higher selectivity；Also, the Co series catalysts neutral component is uniformly dispersed, performance stable and epigranular, applicable The SO in the catalysis flue gas in fixed bed reactors2Reduction sulphur processed, makes SO2Conversion ratio up to more than 90%, selectivity is reachable More than 90%.
Meanwhile, catalyst of the present invention can carry out regeneration treatment after the deactivation, it is only necessary to which in-site secondary is calcined and vulcanized, Catalyst activity can both recover, and improve resource recycling rate.
Applicant states that the present invention illustrates detailed process equipment and the technological process of the present invention by above-described embodiment, But the invention is not limited in above-mentioned detailed process equipment and technological process, that is, do not mean that the present invention has to rely on above-mentioned detailed Process equipment and technological process could be implemented.Person of ordinary skill in the field it will be clearly understood that any improvement in the present invention, Addition, selection of concrete mode of equivalence replacement and auxiliary element to each raw material of product of the present invention etc., all fall within the present invention's Within the scope of protection domain and disclosure.

Claims (10)

1. one kind is used for SO in flue gas2The Co series catalysts of reduction sulphur processed, it is characterised in that the catalyst includes carrier and painting The active component and auxiliary agent being overlying on carrier, wherein active component are Co oxide, and auxiliary agent is Cu, Ni, La, Mg, Ca or Ba In any one or at least two combination of oxides.
2. Co series catalysts according to claim 1, it is characterised in that the carrier is γ-Al2O3, SiO2, TiO2Or Any one in ZSM-5 or at least two combination；
Preferably, the carrier is the homogeneous particle of shape, preferably spherical particle and/or powder.
3. Co series catalysts according to claim 1 or 2, it is characterised in that Co in active component in the catalyst Load capacity is 3wt%~16wt%；
Preferably, Cu load capacity is 1wt%~6wt% in auxiliary agent in the catalyst；
Preferably, Ni load capacity is 1wt%~6wt% in auxiliary agent in the catalyst；
Preferably, La load capacity is 1wt%~6wt% in auxiliary agent in the catalyst；
Preferably, in the catalyst in auxiliary agent Mg load capacity 1wt%~6wt%；
Preferably, in the catalyst in auxiliary agent Ca load capacity 1wt%~6wt%；
Preferably, Ba load capacity is 1wt%~6wt% in auxiliary agent in the catalyst.
4. the preparation method of the Co series catalysts according to claim any one of 1-3, it is characterised in that the preparation method For：Active component and auxiliary agent are carried on carrier using equi-volume impregnating, through drying, roasting and vulcanization, Co systems is made and urge Agent.
5. preparation method according to claim 4, it is characterised in that the preparation method specifically includes following steps：
(1) cobalt source and promoter metal salt are mixed and made into solution；
(2) carrier is added into step (1) described solution, incipient impregnation, the carrier after being impregnated is carried out；
(3) carrier after step (2) described dipping is dried and is calcined, and obtains catalyst precursor；
(4) step (3) described catalyst precursor is vulcanized, obtains Co series catalysts.
6. the preparation method according to claim 4 or 5, it is characterised in that step (1) described cobalt source is cobalt nitrate；
Preferably, step (1) the promoter metal salt is nickel nitrate, copper nitrate, lanthanum nitrate, magnesium nitrate, calcium nitrate or barium nitrate In any one or at least two combination；
Preferably, the consumption of step (1) described cobalt source is：The load capacity for making Co in active component in the catalyst after load is 3wt%~16wt%；
Preferably, the consumption of promoter metal salt is in step (1) described solution：The load capacity for making Cu in the catalyst after load is 1%~6wt%, Ni load capacity are 1%~6wt%, and La load capacity is 1%~6wt%, Mg load capacity 1%~ 6wt%, Ca load capacity 1%~6wt%, Ba load capacity are 1%~6wt%；
Preferably, solvent is water in step (1) described solution.
7. the preparation method according to claim any one of 4-6, it is characterised in that step (2) described carrier be γ- Al2O3, SiO2, TiO2Or any one in ZSM-5 or at least two combination；
Preferably, the time of step (2) described incipient impregnation is 1h~6h；
Preferably, step (3) described drying temperature is 100 DEG C~130 DEG C；
Preferably, step (3) drying time is 1h~6h；
Preferably, the temperature of step (3) described roasting is 400 DEG C~600 DEG C；
Preferably, the time of step (3) described roasting is 6h~12h；
Preferably, step (3) roasting is carried out in Muffle furnace.
8. the preparation method according to claim any one of 4-7, it is characterised in that step (4) vulcanization is in H2S and H2 Mixed atmosphere under carry out；
Preferably, the H2S and H2Mixed atmosphere in H2S volume content is 5%~15%；
Preferably, the temperature of step (4) described vulcanization is 400 DEG C~600 DEG C；
Preferably, the time of step (4) described vulcanization is 0.5h~6h；
Preferably, step (4) vulcanization is carried out in tube furnace.
9. the purposes of the Co series catalysts according to claim any one of 1-3, it is characterised in that by the Co series catalysts For being catalyzed SO in flue gas in fixed bed reactors2Reduction prepares elemental sulfur；
Preferably, SO in the flue gas2Volume content be 20%~30%.
10. purposes according to claim 9, it is characterised in that SO in the catalysis flue gas2Reduction prepares the side of elemental sulfur Method is：
The Co series catalysts are loaded in fixed bed reactors, in discharge system after air, flue gas and coal gas are preheated extremely 300 DEG C~450 DEG C, enter back into fixed bed reactors and reacted at 350 DEG C~450 DEG C, by the SO in flue gas2Reduction system Standby elemental sulfur.
CN201710558187.0A 2017-07-10 2017-07-10 A kind of cobalt series catalyst that sulphur processed is reduced for sulfur dioxide in flue gas and its production and use Pending CN107175108A (en)

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CN109354149A (en) * 2018-11-12 2019-02-19 昆明理工大学 A kind of processing method of the waste water containing heavy metal-polluted acid
CN110787813A (en) * 2019-10-21 2020-02-14 北京北大先锋科技有限公司 Coal-fired flue gas-based SO2Catalyst for preparing elemental sulfur by catalytic reduction and preparation method
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CN112569953A (en) * 2020-12-02 2021-03-30 宁波中科远东催化工程技术有限公司 Desulfurization catalyst and preparation method thereof
CN114609323A (en) * 2020-12-09 2022-06-10 中国石油天然气集团有限公司 Method for evaluating continuous reforming catalyst
CN115155628A (en) * 2022-07-29 2022-10-11 南京工业大学 Carbon-based desulfurization catalyst, preparation method and application
CN115155628B (en) * 2022-07-29 2023-10-20 南京工业大学 Carbon-based desulfurization catalyst and preparation method and application thereof

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Application publication date: 20170919