CN1108862C - Flue gas purifying catalyst - Google Patents
Flue gas purifying catalyst Download PDFInfo
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- CN1108862C CN1108862C CN00107487A CN00107487A CN1108862C CN 1108862 C CN1108862 C CN 1108862C CN 00107487 A CN00107487 A CN 00107487A CN 00107487 A CN00107487 A CN 00107487A CN 1108862 C CN1108862 C CN 1108862C
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Abstract
The present invention relates to a compound oxide catalyst which can simultaneously eliminate oxynitride, sulfur oxide and carbon monoxide in smoke gas. The compound oxide catalyst is prepared from magnesium, aluminum and composite oxides containing at least one of transition metal elements and at least one of rare earth metal elements. The catalyst is made by calcining lamellar matters having hydrotalcite structure and containing Mg, Al and transition metal elements, and mixtures of rare earth hydrated oxide, and the catalyst can simultaneously eliminate oxynitride, sulfur oxide and carbon monoxide in smoke gas, and has excellent hydrothermal stability.
Description
The present invention relates to a kind ofly can reduce the industrial smoke for example flue gas in the oil plant FCC regenerator and the catalysis conversion method of nitrogen oxide, oxysulfide and carbon monoxide emission in fire coal boiler fume or the vehicle exhaust simultaneously.
Fluid catalytic cracking (FCC) is one of main method of refinery's production gasoline, diesel oil etc.FCC apparatus mainly comprises reactor and regenerator; Feedstock oil is delivered into the riser of reactor, is cracked into distillate by contacting with the FCC catalyst mix; Simultaneously, catalyst is because of the green coke inactivation; Catalyst behind the inactivation carries out coke burning regeneration through being sent to regenerator behind the stripping; Contained nitrogen compound and sulphur compound (coming from feedstock oil) are oxidized to nitrogen oxide (NOx) and oxysulfide (SOx), hydrogeneous generation water in the coke in the coke.Nitrogen oxide in the FCC regenerator flue gas mainly is nitric oxide (about 90 volume %), contains a spot of nitrogen dioxide simultaneously.Generally in 480-570 ℃ of scope, regenerator temperature is between 650-760 ℃ for the FCC temperature of reactor.The concentration of nitrogen oxide is 50-500ppmv in the regenerator, and the concentration of carbon monoxide is subjected to FCC effects of operation conditions excursion bigger.Carbon monoxide content is very high during imperfect combustion, and concentration is then very low when adopting combustion adjuvant completing combustion.Even but under the situation of completing combustion, the regenerator dense-phase bed still has higher carbonomonoxide concentration.Similarly, also contain a large amount of nitrogen oxide, carbon monoxide and/or oxysulfide in coal-burning boiler flue gas and the vehicle exhaust.
Nitrogen oxide can damage the ozone layer, and nitrogen oxide and oxysulfide can form acid rain, the grievous injury earth environment; Carbon monoxide also is main air pollutants.Therefore it is significant to improving environment for human survival to study the method that removes nitrogen oxide in the flue gas, oxysulfide and carbon monoxide.
Method about nitrogen oxide and carbon monoxide emission in the reduction fire coal boiler fume has more patent report.For example, by in flue gas, injecting the hydrocarbon thing of ammonia or low carbon chain; Under the situation that oxygen exists, pass through V
2O
5/ TiO
2Deng the catalytic action of catalyst, can make the nitrogen oxide in the flue gas in 150-400 ℃ temperature range, reduce to very low level.But because high regeneration temperature and other harsh operating condition in the FCC regenerator, these methods generally are unsuitable for FCC apparatus.
USP4,973,399 and USP4,980,052 have introduced a kind of catalyst of the FCC of minimizing regenerator discharged nitrous oxides, wherein contain molecular sieve and the titanium dioxide or the zirconia component of copper exchange.Under suitable condition, its removal of nitrogen oxide rate can reach 79%.
USP5,085,762 method that proposes is that the MCM-22 with load copper, cerium, titanium makees catalyst, the effect of cerium, titanium mainly is the hydrothermal stability of improvement Cu/MCM-22.700 ℃, 100%H
2The catalyst of O hydrothermal aging after 4 hours can be with the removal of nitrogen oxide in the FCC regenerator flue gas 60%.
USP5,002,654 and USP4,988,432 have described the method that reduces discharged nitrous oxides in the FCC regenerator with zinc oxide and antimony oxide catalyst respectively.But only be applicable to the FCC apparatus of processing low sulfur content and low-metal content, medium nitrogen content feedstock oil.
USP5,364,517 have described a kind of perovskite and the combined group of spinelle method of assigning to reduce discharged nitrous oxides in the FCC regenerator with cupric.
USP5,591,418 have described adsorbent of a kind of FCC of removing flue gas sulphur oxide or nitrogen oxide and preparation method thereof; This adsorbent is made up of very thin crystallite, its key component is to contain the impurity in the single oxide that is dispersed in divalent metal such as the solid solution of aluminium oxide, and contain the crystallite of spinelle crystallite and trivalent metal, wherein divalent metal is selected from magnesium, calcium, zinc, barium and strontium, trivalent metal is selected from cerium, lanthanum, iron, chromium, vanadium and cobalt, also contains oxide and the anion of V, W or Mo in addition; Its preparation method is the first hopcalite of preparation divalent metal, aluminium and trivalent metal, the metavanadic acid radical ion in the adsorbent solution or tungsten, molybdenum acid ion again after the roasting, and then roasting.This adsorbent is mainly used in the desulfurization oxide, and can be nitrogen with conversion of nitrogen oxides.
USP3,835,031st, add in the Cracking catalyst reducing the release of oxysulfide about metal oxide (CaO or MgO), and successfully developed a kind of desulfurization oxide addition in 1977 with IIA family, this is a desulfurization oxide addition the earliest.
USP4,071,436,4,166,787,4,243,556 have introduced and have used various Al
2O
3Do the desulfurization oxide addition.
USP4,469,589th, use load C eO
2The Mg-Al spinelle do the desulfurization oxide addition and be used for industrial production.
USP4,963,520 have introduced a kind of like this desulfurization oxide catalyst, with the magnalium ratio is 0.77, the spinelle of the about 65 μ m of particle diameter is load C e respectively, Pr, La, Fe, Mn, Co, V, metal or two kinds of metals of load simultaneously such as Sn, then the spinelle after the load is mixed with industrial catalyst, use in pilot-plant to observe the desulfurization situation, spinelle accounts for 1.25 weight % of mixed catalyst, and feed sulphur content is 2 weight %, test condition is: 537 ℃ of temperature of reactor, 693 ℃ of regenerator temperature, 499 ℃ of stripping section temperature, 30 minutes catalyst regeneration time, oil ratio is 6, and weight (hourly) space velocity (WHSV) is 10 hours
-1The result shows that in the spinelle of difference load C e, Pr, La, Fe, Mn, Co, V, Sn, the fresh dose of desulfuration efficiency of load C e is up to 83%, secondly be 81% when carrying V, but after accelerated ageing two days later (simulation industrial condition), desulfurization oxide efficient is reduced to below 50%, during two kinds of metals of load simultaneously, the desulfurization oxide of V/Ce/ spinelle is most effective, and (fresh dose is 96%, after aging is 78%), but owing to the intoxication of V to the FCC catalyst, should not use.
USP4,957,718 have prepared perovskite-like material: MgMnO
3, La
0.8Mg
0.2MnO
3, La
0.2Mg
0.8MnO
3, La
0.8Mg
0.2CoO
3, La
0.5Mg
0.5CoO
3, La
0.8Mg
0.3FeO
3, respectively its desulfurization oxide performance being tested, the result shows, under the oxygen enrichment situation, along with the increase of cycle-index, the very fast decline of the efficient of trap sulfur oxide (after 5 circulations, La
0.2Mg
0.8MnO
3Capture rate drop to 32% by 96%).
USP5,057,205 usefulness magnesium aluminate spinel is made the desulfurization oxide addition, is used as matal deactivator simultaneously, and the raw material high to tenor more can play a role.The solid solution that magnesium aluminate spinel and magnesia are formed, a certain amount of Ce or La in the load are very effective desulfurization oxide additions and catch the V agent, and are of value to the raising gasoline selective, reduce green coke and amounts of hydrogen, Ce, La are used to promote SO
2To SO
3Conversion.
USP5,288,675 usefulness coprecipitations have prepared the ternary oxide of non-spinelle, mainly are MgO/La
2O
3/ Al
2O
3And MgO/RE
2O
3/ Al
2O
3, oxysulfide capture performance is better than the Mg/Al/ spinelle by the composite oxides of this non-spinel structure of test specification
USP5,750,020 have introduced the preparation method of a kind of desulfurization oxide or nitrogen oxide catalyst.The mixture that at first prepares hydrotalcite and cerium oxide, the metavanadic acid radical ion in the adsorbent solution again after the roasting, and then roasting.Hydrothermal stability and antioxygen to catalyst in the patent are not considered, and can not be removed oxysulfide and nitrogen oxide simultaneously.
The method that reduces carbon monoxide in the regenerator flue gas normally adds CO combustion promoter.About CO combustion promoter a large amount of patent reports is arranged.
USP2, the chromium oxide that proposes in 647,860 to add the heavy % of 0.1-1 promote the conversion of carbon monoxide to carbon dioxide, and prevent after-burning in the FCC catalyst.USP3,788,977 suggestions load on the aluminium oxide Pt as matrix components or directly it are joined in the FCC catalyst, promote the completing combustion of carbon monoxide.USP4,251,395, USP4,265,787, USP4,008,568, USP4,072,600, USP4,093,535, USP4,159,239 grades all are the composition of relevant CO combustion promoter and the patent of application thereof.Use CO combustion promoter, carbon monoxide discharges and the problem of after-burning though can solve, and can not solve the emission problem of nitrogen oxide, even also can increase the discharging of nitrogen oxide.
USP4,199,435 adopt the way of passivation CO combustion promoter, reduce the influence that it generates nitrogen oxide, and its method is at combustion adjuvant (0.2 heavy %Pt/Al
2O
3) before the use, earlier its hydrothermal aging under 980 ℃ of left and right sides normal pressures was re-used in 96 hours.USP4,235,704 adopt the method passivation CO combustion promoter that adds antimony or tin, reach the purpose of the discharging that reduces FCC regenerator nitrogen oxide with this.But adopt the way of passivation CO combustion promoter to reduce the utilization ratio of combustion adjuvant, thereby increased the discharging of carbon monoxide.
USP4,300,997 and USP4, propose in 350,615 to make CO combustion promoter with Pd-Ru, this combustion adjuvant is compared with other combustion adjuvant, when promoting CO burning, can reduce the growing amount of nitrogen oxide in the FCC regenerator, but these use the catalyst cost of noble metal higher.
The catalyst that is used for removing the nitrogen oxide of vehicle exhaust also has many patent reports, and it is the part active component that these catalyst mostly adopt noble metal.
The purpose of this invention is to provide a kind of gas cleaning catalysis conversion method that can effectively remove nitrogen oxide, oxysulfide and carbon monoxide simultaneously.
The mechanism of catalytic purification flue gas of the present invention is: utilize the characteristics of NOx and CO coexistence in the dense-phase bed, make the reducing agent of NOx with CO, simultaneously with carbon monoxide and conversion of nitrogen oxides, and catalyst used in the present invention can be efficiently with SO
2Be converted into SO
3, SO
3Again with catalyst in magnesium generate Sulfates and be adsorbed, and under reducing condition, be reduced and make the catalyst effective regeneration.Transition metal and rare earth synergy, the effect of transition metal mainly is to transform CO and NOx; Rare earth plays synergy to Cu on the one hand, makes transition metal be difficult for being poisoned by SOx, on the other hand can be with SO
2Be converted into SO
3And absorbed by Mg.
Catalysis conversion method provided by the present invention is to make the flue gas that contains nitric oxide, oxysulfide and carbon monoxide in 300-800 ℃ of scope, especially contacts with a kind of specific catalyst in 400-750 ℃ of scope.
The catalyst that removes nitrogen oxide in the flue gas, oxysulfide and carbon monoxide used in the present invention is made up of the composite oxides of magnesium, aluminium, at least a transition metal and at least a thulium; Its anhydrous chemical expression is mMgOnAl
2O
3XMO
A/2YRE
2O
3Wherein M is a kind of in the transition metal that is selected from the group of being made up of Zn, Co, Ni, Cu, Fe, Cr or two kinds, wherein preferred Cu or Fe; RE comprises a kind of in the thulium of lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), or based on the mixed rare-earth elements of La and/or Ce, wherein preferably La, Ce or based on the mixed rare-earth elements of La and/or Ce, more preferably La or Ce; A is the valence state (its value is 2 or 3) of M; The value of m/n is greater than 2 to less than 30, preferably m/n=3-10; X/ (m+n+x+y)=0.001-0.15, preferred 0.005-0.08; Y/ (m+n+x+y)=0.001-0.1, preferred 0.003-0.05.
Catalyst used in the present invention is made through roasting by the mixture of bedded substance that contains Mg, Al and transition metal with hydrotalcite structure and rare earth hydrous oxide, the condition of said roasting is that temperature is 300-1100 ℃, preferred 450-900 ℃, more preferably 500-800 ℃, roasting time is 1-15 hour, preferred 2-10 hour.
Preparation of catalysts method used in the present invention can be:
(1), required ratio is dissolved in the salt compounds of magnesium, aluminium, transition metal and rare earth metal in the distilled water in the definition according to the invention described above catalyst, the total concentration that makes metal ion is between 0.5-2.5M, preferred 1-1.5M obtains the mixed solution of slaine; The anion of said slaine is optional from sulfate ion, nitrate ion, carbanion, acetate ion, chlorion etc.; Wherein preferred carbanion;
(2), according to a certain percentage prepare the mixed ammonium/alkali solutions of sodium carbonate and NaOH, sodium carbonate is 10-20 with the ratio of the mole of NaOH: 1, and preferred 12-18: 1;
(3), under agitation mixed solution and the said mixed ammonium/alkali solutions with said slaine adds in a certain amount of water with certain speed respectively, the amount of said water has no particular limits, and doubly is advisable with the 0.2-2 of the mixed liquor volume of said slaine; The adding speed of salting liquid and aqueous slkali is so that the pH of mixing rear slurry is controlled between the 7.5-13, and being preferably between the 8.5-11 is standard; The consumption of said mixed ammonium/alkali solutions has no particular limits, and being controlled at 7.5-13 with the pH with the mixed slurries of two solution is standard; The temperature of distilled water can be preferably between 40-90 ℃ between room temperature-110 ℃;
(4), with step (3) gained slurry water thermal crystallisation, crystallization temperature is between 25-110 ℃, preferred 40-90 ℃; Crystallization time was preferably between 1-8 hour between 0.5-24 hour; Then the product after the crystallization is filtered, washs, the pH value of cleaning solution should be near 7 when washing was finished; It is dry according to a conventional method to wash back gained filter cake;
(5), step (4) products therefrom is carried out roasting, the condition of roasting is that temperature is 300-1100 ℃, preferred 450-900 ℃, and more preferably 500-800 ℃; Time is 1-15 hour, preferred 2-10 hour.
Said rare earth element also can be introduced by dipping or as the form of carrier except introducing with the form of co-precipitation.
Fig. 1 be among the embodiment 1 preparation after drying and the X-ray diffractogram of sample before the roasting, wherein " o " is the diffraction maximum of hydrotalcite, " * " is CeO
2Diffraction maximum.
Fig. 2 is the X-ray diffractogram of gained catalyst A after the roasting among the embodiment 1, and wherein " * " is CeO
2The peak, " v " is the peak of MgO.
The characteristics that remove the catalyst of nitrogen oxides in effluent, oxysulfide and carbon monoxide used in the present invention are, carbon monoxide in its use procedure in the available flue gas is made reducing agent, when reduction of nitrogen oxide is nitrogen, carbon monoxide is oxidized to carbon dioxide, reaches the purpose that removes simultaneously nitrogen oxide and carbon monoxide.
The characteristics of catalyst used in the present invention are that also this catalyst when nitric oxide and reaction of carbon monoxide are had high catalytic activity, has hydrophily, that is to say that under the condition of high temperature hydro-thermal, its catalytic activity is higher.
Catalysis conversion method provided by the invention aspect such as nitrogen oxide and carbon monoxide in reducing vehicle exhaust, coal-burning boiler flue gas and FCC regenerator flue gas all has application prospect.
The following examples will the present invention is described further.Wherein the surface area of catalyst and pore volume are measured with the GB/T5816-1995 standard method.
Embodiment 1
The Preparation of catalysts that present embodiment explanation the present invention uses.
25.9 gram magnesium nitrate hexahydrates, 14.1 grams, nine water aluminum nitrates, 2.25 gram six water cerous nitrates and 1.125 grams, one water acetic acid copper are dissolved in 100 milliliters 65 ℃ the distilled water, as salting liquid; Take by weighing 13.5 gram NaOH and 14.3 gram washing sodas are dissolved in 100 milliliters 65 ℃ the distilled water, as aqueous slkali; The beaker that fills 100 ml distilled waters is placed 65 ℃ water bath with thermostatic control, under agitation simultaneously above-mentioned salting liquid and above-mentioned aqueous slkali are splashed in this beaker, control the speed of dripping of two solution, the pH value that makes solution is all the time about 9.5.After dripping off two solution, the gained mixture is continued to stir 15 minutes, left standstill then aging 4 hours.The pH value that filters and be washed with water to cleaning solution is 7.Filter cake is following dry 12 hours at 120 ℃; Then with products therefrom 750 ℃ of roastings 3 hours.The gained catalyst is designated as catalyst A, measures its specific surface and pore volume with the nitrogen adsorption method.The composition and the character of catalyst A are listed in the table 1.
Embodiment 2
The Preparation of catalysts that present embodiment explanation the present invention uses.
25.9 gram magnesium nitrate hexahydrates, 14.1 grams, nine water aluminum nitrates, 0.9 gram six water cerous nitrates and 1.125 grams, one water acetic acid copper are dissolved in 100 milliliters 65 ℃ the distilled water, as salting liquid; Prepare catalyst according to condition and the step identical then with embodiment 1.The gained catalyst is designated as catalyst B, and its composition and character are listed in the table 1.
Embodiment 3
The Preparation of catalysts that present embodiment explanation the present invention uses
25.9 gram magnesium nitrate hexahydrates, 14.1 grams, nine water aluminum nitrates, 0.3 gram six water cerous nitrates and 1.125 grams, one water acetic acid copper are dissolved in 100 milliliters 65 ℃ the distilled water, as salting liquid; Prepare catalyst according to condition and the step identical with embodiment 1 then, different is that roasting condition is 550 ℃ of roastings 7 hours.The gained catalyst is designated as catalyst C, and its composition and character are listed in the table 1.
Embodiment 4
The Preparation of catalysts that present embodiment explanation the present invention uses.
With 25.9 gram magnesium nitrate hexahydrates, 14.1 grams, nine water aluminum nitrates, 1.8 grams, six water cerous nitrates, and 1.8 grams, one water acetic acid copper is dissolved in 100 milliliters 65 ℃ the distilled water, as salting liquid; Prepare catalyst according to condition and the step identical then with embodiment 1.The gained catalyst is designated as catalyst D, and its composition and character are listed in the table 1.
Embodiment 5
The Preparation of catalysts that present embodiment explanation the present invention uses.
With 25.9 gram magnesium nitrate hexahydrates, 14.1 grams, nine water aluminum nitrates, 1.8 gram six water cerous nitrates and 1.125 grams, one water acetic acid copper, be dissolved in 100 milliliters 65 ℃ the distilled water, as salting liquid; Prepare catalyst according to condition and the step identical with embodiment 1 then, different is that roasting condition is 800 ℃ of roastings 2 hours.The gained catalyst is designated as catalyst E, and its composition and character are listed in the table 1.
Embodiment 6
The Preparation of catalysts that present embodiment explanation the present invention uses.
25.9 gram magnesium nitrate hexahydrates, 14.1 grams, nine water aluminum nitrates, 1.8 gram six water cerous nitrates and 0.563 gram, one water acetic acid copper are dissolved in 100 milliliters 65 ℃ the distilled water, as salting liquid; Prepare catalyst according to condition and the step identical then with embodiment 1.The gained catalyst is designated as catalyst F, and its composition and character are listed in the table 1.
Table 1
| The embodiment numbering | The catalyst numbering | Form heavy % | Surface area (rice 2/ gram) | Pore volume (milliliter/gram) | ||||
| Na 2O | MgO | Al 2O 3 | CuO | CeO 2 | ||||
| 1 | A | 0.07 | 53.9 | 27.2 | 7.5 | 11.3 | 168 | 0.71 |
| 2 | B | 0.05 | 58.1 | 28.5 | 7.7 | 5.6 | 159 | 0.59 |
| 3 | C | 0.05 | 60.6 | 29.7 | 7.9 | 1.7 | 155 | 0.63 |
| 4 | D | 0.03 | 52.9 | 26.8 | 11.4 | 8.8 | 178 | 0.90 |
| 5 | E | 0.08 | 57.2 | 26.6 | 7.4 | 8.7 | 183 | 0.93 |
| 6 | F | 0.04 | 59.3 | 27.5 | 4.1 | 9.0 | 195 | 0.97 |
Embodiment 7
The Preparation of catalysts that present embodiment explanation the present invention uses.
25.9 gram magnesium nitrate hexahydrates, 12.0 grams, nine water aluminum nitrates, 2.44 gram six water cerous nitrates and 4.55 grams, nine water ferric nitrates are dissolved in 100 milliliters 65 ℃ the distilled water, as salting liquid; Prepare catalyst according to condition and the step identical then with embodiment 1.The gained catalyst is designated as catalyst G, and its composition and character are: Na
2The heavy % of O:0.01, the heavy % of MgO:54.1, Al
2O
3: 22.1 heavy %, CeO
2: 12.5 heavy %, Fe
2O
3: 11.2 heavy %; Specific surface: 141 meters
2/ gram, pore volume: 0.54 milliliter/gram.
Embodiment 8
The Preparation of catalysts that present embodiment explanation the present invention uses.
25.9 gram magnesium nitrate hexahydrates, 12.0 grams, nine water aluminum nitrates, 2.44 gram six water cerous nitrates and 3.35 gram zinc nitrate hexahydrates are dissolved in 100 milliliters 65 ℃ the distilled water, as salting liquid; Prepare catalyst according to condition and the step identical then with embodiment 1.The gained catalyst is designated as catalyst H, and its composition and character are: Na
2The heavy % in O＜0.01, the heavy % of MgO:53.6, Al
2O
3: 21.4 heavy %, CeO
2: 12.8 heavy %, the heavy % of ZnO:12.1; Specific surface: 156 meters
2/ gram, pore volume: 0.63 milliliter/gram.
Embodiment 9
The Preparation of catalysts that present embodiment explanation the present invention uses.
25.9 gram magnesium nitrate hexahydrates, 12.0 grams, nine water aluminum nitrates, 2.44 gram lanthanum nitrate hexahydrates and 2.25 grams, one water acetic acid copper are dissolved in 100 milliliters 65 ℃ the distilled water, as salting liquid; Prepare catalyst according to condition and the step identical then with embodiment 1.The gained catalyst is designated as catalyst I, and its composition and character are: Na
2The heavy % in O＜0.01, the heavy % of MgO:54.1, Al
2O
3: 21.6 heavy %, La
2O
3: 12.3 heavy %, the heavy % of CuO:12.0; Specific surface: 171 meters
2/ gram, pore volume: 0.65 milliliter/gram.
The Preparation of catalysts that present embodiment explanation the present invention uses
28.8 gram magnesium nitrate hexahydrates, 14.06 gram nine water aluminum nitrates and 2.25 grams, one water acetic acid copper are dissolved in 100 milliliters 65 ℃ the distilled water, as salting liquid; Take by weighing 13.5 gram NaOH and 14.3 gram washing sodas are dissolved in 100 milliliters 65 ℃ the distilled water, as aqueous slkali; (it consists of: La to take by weighing 2.1 gram bastnasites
2O
326 weight %, CeO
246.9 weight %, Nd
2O
37.0 weight %, Pr
6O
114.9% weight %) puts into the beaker that fills 100 ml distilled waters, this beaker placed 65 ℃ water bath with thermostatic control, under agitation simultaneously above-mentioned salting liquid and above-mentioned aqueous slkali are splashed in this beaker, control the speed of dripping of two solution, the pH value that makes solution is all the time about 9.5.After dripping off two solution, the gained mixture is continued to stir 15 minutes, left standstill then aging 4 hours.The pH value that filters and be washed with water to cleaning solution is 7.Filter cake is following dry 12 hours at 120 ℃; Then with products therefrom 750 ℃ of roastings 3 hours.The gained catalyst is designated as catalyst J, and its composition and character are listed in and is Na
2The heavy % in O＜0.01, MgO 47.8 heavy %, Al
2O
320.2 heavy %, CuO 9.6 heavy %, La
2O
35.8 weight %, CeO
210.5 weight %, Nd
2O
31.6 weight %, Pr
6O
111.1% weight %, specific surface: 162 meters
2/ gram, pore volume: 0.59 milliliter/gram.
Comparative Examples 1
The explanation of this Comparative Examples does not contain the comparative catalyst's of transition metal preparation.
28.8 gram magnesium nitrate hexahydrates, 13 gram nine water aluminum nitrates and 1.25 grams, six water cerous nitrates are dissolved in 100 milliliters 65 ℃ the distilled water, as salting liquid; Prepare catalyst according to condition and the step identical then with embodiment 1.The gained catalyst is designated as catalyst K, and it consists of Na
2O 0.05 heavy %, the heavy % of MgO:59.8, Al
2O
3: 25 heavy %, CeO
2: 15 heavy %; Specific surface: 105 meters
2/ gram, pore volume: 0.34 milliliter/gram.
Comparative Examples 2
The explanation of this Comparative Examples does not contain the comparative catalyst's of rare earth element preparation.
2.25 grams, one water acetic acid copper, 25.9 gram magnesium nitrate hexahydrates and 14.06 grams, nine water aluminum nitrates are dissolved in 100 milliliters 65 ℃ the distilled water, as salting liquid; Prepare catalyst according to condition and the step identical then with embodiment 1.The gained catalyst is designated as catalyst L, and it consists of Na
2The heavy % in O＜0.01, the heavy % of MgO:49.8, Al
2O
3: 29 heavy %, the heavy % of CuO:21; Specific surface: 161 meters
2/ gram, pore volume: 0.76 milliliter/gram.
Embodiment 11
The preparation of the hydrothermal aging sample of the catalyst that present embodiment explanation the present invention uses.
Catalyst A, G under the condition of 800C, 100% water, are carried out hydrothermal aging respectively; The character such as the table 2 of ageing time and ageing products.
Table 2
| Catalyst | The hydrothermal aging time, hour | Aging back sample number into spectrum | Specific surface rice 2/ gram | Pore volume milliliter/gram |
| A | 4 | A-1 | 80 | 0.51 |
| 17 | A-2 | 65 | 0.43 | |
| G | 4 | G-1 | 72 | 0.49 |
| 17 | G-2 | 60 | 0.38 |
Embodiment 12-23
These embodiment illustrate that catalyzed conversion provided by the invention takes off the effect of nitric oxide and carbon monoxide.
Catalyst is made the particle of 350-800 micron grain size in advance.Catalyst is packed in the fixed bed reactors (tube inner diameter is 6 millimeters), feed carrier gas (argon gas) and be heated to reaction temperature and purge half an hour, keeping (controlling) under the constant situation of total gas flow rate to wherein feeding reacting gas then by adjusting carrier gas flux, with the online detection nitrous oxides concentration of QGS-08B type infrared analyzer (wheat Haake Analytical Instrument Co., Ltd of Beijing Analytical Instrument Factory commercial product), with the two online detection carbon monoxide of gas circuit gas-chromatography of GC-8APT twin columns, nitrogen, oxygen, sulfur dioxide, concentration of carbon dioxide.Gas flow is by the mass flow controller control of Brooks company.
Said conversion ratio is the conversion ratio of percentage concentration calculating by volume.Reaction condition:
Argon gas is done carrier gas, and total gas flow rate is 400 standard cubic centimeters per minute
Reaction temperature: 720 ℃
Reaction pressure: normal pressure
Catalyst useful load: 150 milligrams
NO → N when table 3 is the differential responses condition
2Conversion ratio, comprise following 4 kinds of reaction systems: reaction system 1: unstripped gas comprises NO, CO and Ar, nitric oxide (NO) concentration is 600ppm (body
Long-pending), carbon monoxide (CO) concentration is 1.4% (volumetric concentration), it is 1 little to ventilate continuously
The time after the nitric oxide conversion ratio that changes into nitrogen be expressed as R
1Reaction system 2: in system 1, feed O
2, oxygen (O
2) concentration is 0.5% (volumetric concentration), R
2
Expression feeds O
2Nitric oxide changes into the conversion ratio of nitrogen after 1 hour; Reaction system 3: feed steam in system 2, water vapour content is 3% (volumetric concentration), R
3Table
Show feed steam after 1 hour nitric oxide change into the conversion ratio of nitrogen; Reaction system 4: in system 3, feed SO
2, sulfur dioxide (SO
2) concentration is that (volume is dense for 500ppm
Degree), R
4Expression feeds SO
2Nitric oxide changes into the conversion ratio of nitrogen after 1 hour; R
5CO → CO under expression reaction system 4 conditions
2Conversion ratio.
Table 3
| Embodiment | Catalyst | R 1，％ | R 2，％ | R 3，％ | R 4，％ | R 5，％ |
| 12 | A | 100 | 97.8 | 97.2 | 95.6 | 100 |
| 13 | B | 100 | 96.2 | 96.5 | 92.9 | 100 |
| 14 | C | 100 | 95.5 | 94.1 | 89.2 | 100 |
| 15 | D | 100 | 97.1 | 96.8 | 95.2 | 100 |
| 16 | E | 100 | 96.1 | 96.1 | 94.9 | 100 |
| 17 | F | 100 | 94.6 | 95.1 | 94.6 | 100 |
| 18 | G | 100 | 94.2 | 92.5 | 82.8 | 100 |
| 19 | H | 91.2 | 89.6 | 79.8 | 69.5 | 89.7 |
| 20 | I | 100 | 90.5 | 87.4 | 82.9 | 100 |
| 21 | J | 97.3 | 85.7 | 72.6 | 21.2 | 75.7 |
| 22 | K | 94.3 | 74.2 | 76.1 | 11.4 | 75.7 |
| 23 | L | 70.1 | 48.5 | 85 | 20.7 | 73.8 |
Embodiment 24-27
These embodiment illustrate that catalysis conversion method provided by the invention removes the effect of nitric oxide performance.
Catalyst A-1, A-2, G-1, G-2 be by catalyst A, G by embodiment 17 through 800 ℃, 100%H
2O obtained in aging 4 hours or 17 hours.Test and reaction condition are with embodiment 12-23, and test result is listed in the table 4.
Table 4
| Embodiment | Catalyst | R 1，％ | R 2，％ | R 3，％ | R 4，％ | R 5，％ |
| 24 | A-1 | 100 | 97.8 | 97.2 | 95.6 | 100 |
| 25 | A-2 | 100 | 97.8 | 97.2 | 95.6 | 100 |
| 26 | G-1 | 100 | 93.1 | 93.5 | 81.4 | 100 |
| 27 | G-2 | 100 | 91.9 | 93.7 | 80.3 | 100 |
Embodiment 28-40
Present embodiment illustrates that catalysis conversion method provided by the invention removes the effect of oxysulfide.
The performance of catalyst absorption SOx and the regeneration situation after the absorption are measured by DTG on the TA2100 thermal analyzer.Adsorption conditions is: SO
2(0.5% (V))+O
2+ Ar, total gas flow rate are 200SCCM, and the catalyst useful load is 20mg, and adsorption temp is 720 ℃.Catalyst behind the absorption SOx is used hydrogen reducing under adsorption temp, reducing condition is: H
2(20% (V))+Ar, total gas flow rate is 200SCCM, reduction temperature is 550 ℃.Adsorption capacity represents that with the SOx adsorption capacity test result is listed in the table 5.Hydrogen reducing performance (power of regeneration of promptly adsorbing the SOx rear catalyst) is used H
2Reduction degree represents that test result is listed in the table 6.
Table 5
| Embodiment | Catalyst | Oxysulfide adsorption capacity (%) | ||
| 350℃ | 550℃ | 720℃ | ||
| 28 | A | 6.53 | 45.15 | 81.8 |
| 29 | B | 4.97 | 29.30 | 85.11 |
| 30 | C | 4.13 | 21.15 | 67.90 |
| 31 | D | 6.23 | 40.31 | 63.49 |
| 32 | E | 4.97 | 36.00 | 67.00 |
| 33 | F | 6.33 | 40.24 | 73.15 |
| 34 | K | 5.14 | 44.32 | 73.06 |
| 35 | L | 6.12 | 29.02 | 74.91 |
| 36 | A-1 | - | 15.81 | 63.40 |
| 37 | A-2 | - | 15.99 | 67.94 |
Table 6
| Example number | Catalyst | Hydrogen reducing degree (%) | ||
| 350℃ | 550℃ | 720℃ | ||
| 38 | A | 13.29 | 63.42 | 96.54 |
| 39 | K | 9.52 | 45.24 | 90.05 |
| 40 | L | 9.97 | 59.67 | 97.22 |
Claims (9)
1, a kind of catalysis conversion method that removes nitrogen oxide in the flue gas, oxysulfide and carbon monoxide, it is characterized in that making flue gas to contact with a kind of catalyst of being made up of the composite oxides of magnesium, aluminium, at least a transition metal and at least a thulium down at 300～800 ℃, the anhydrous chemical expression of this catalyst is mMgOnAl
2O
3XMO
A/2YRE
2O
3Wherein M is a kind of in the transition metal that is selected from the group of being made up of Zn, Co, Ni, Cu, Fe, Cr or two kinds; RE comprises a kind of in the thulium of lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), or based on the mixed rare-earth elements of La and/or Ce; A is the valence state (its value is 2 or 3) of M; The value of m/n is to less than 30 greater than 2; X/ (m+n+x+y)=0.001-0.15; Y/ (m+n+x+y)=0.001-0.1.
2,, it is characterized in that flue gas is 400～750 ℃ with the temperature that contacts of catalyst according to the catalysis conversion method of claim 1.
3,, it is characterized in that this catalyst is made through roasting by the mixture of bedded substance that contains Mg, Al and transition metal with hydrotalcite structure and rare earth hydrous oxide according to the catalysis conversion method of claim 1.
4, according to the catalysis conversion method of claim 3, wherein the condition of said roasting is that temperature is 450-900 ℃, and the time is 1-15 hour.
5, according to the catalysis conversion method of claim 4, wherein the condition of said roasting is that temperature is 500-800 ℃, and the time is 2-10 hour
6, according to the catalysis conversion method of claim 1, M wherein is Cu or Fe.
7, according to the catalysis conversion method of claim 1, RE wherein is La, Ce or based on the mixed rare-earth elements of La and/or Ce.
8, according to the catalysis conversion method of claim 7, RE wherein is La or Ce.
9, according to the catalysis conversion method of claim 1, m/n=3-10 wherein; X/ (m+n+x+y)=0.005-0.08; Y/ (m+n+x+y)=0.003-0.05.
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| CN99107786.5 | 1999-05-28 | ||
| CN00107487A CN1108862C (en) | 1999-05-28 | 2000-05-19 | Flue gas purifying catalyst |
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| CN1688508A (en) * | 2002-08-13 | 2005-10-26 | 英特凯特公司 | Flue gas treatments to reduce NOx and CO emissions |
| ZA200604817B (en) * | 2003-12-05 | 2007-12-27 | Interact Inc | Mixed metal oxide sorbents |
| CN100368081C (en) * | 2005-07-15 | 2008-02-13 | 山东大学 | Natural gas partial oxidation catalyst prepared by making hydrotalcite as predecessor |
| CN100430114C (en) * | 2006-12-30 | 2008-11-05 | 东北大学 | Device and method for denitrifying smoke using magnesium oxide to catalyze adsorbant |
| CN102895873B (en) * | 2011-07-28 | 2014-10-29 | 中国石油化工股份有限公司 | Method for simultaneously removing sulfur oxides, nitrogen oxides and carbon monoxide in flue gas |
| US9266062B2 (en) | 2011-07-28 | 2016-02-23 | China Petroleum & Chemical Corporation | Method of removing sulfur oxides and nitrogen oxides in the flue gas |
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| CA2865393C (en) * | 2012-02-23 | 2021-03-16 | Johnson Matthey Process Technologies, Inc. | Process of removing nox from flue gas |
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| EP3398678A1 (en) * | 2017-05-05 | 2018-11-07 | SASOL Germany GmbH | Nox trap catalyst support material composition |
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| CN109529860A (en) * | 2018-12-04 | 2019-03-29 | 云南大学 | A kind of X-Sn-Zr reducing catalyst and its preparation method and application |
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| CN115779922A (en) * | 2021-09-09 | 2023-03-14 | 中国石油化工股份有限公司 | Structured catalyst and preparation method thereof and simultaneous SO removal of flue gas X And NO X Method (2) |
| CN113856736B (en) * | 2021-09-14 | 2023-09-26 | 常州大学 | Catalyst for catalytic oxidation of thiophene in diesel oil, and preparation method and application thereof |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999003779A1 (en) * | 1997-07-21 | 1999-01-28 | Bp Amoco Corporation | Method of hydrocarbon reforming and catalyst and catalyst precursor therefor |
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| WO1999003779A1 (en) * | 1997-07-21 | 1999-01-28 | Bp Amoco Corporation | Method of hydrocarbon reforming and catalyst and catalyst precursor therefor |
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