CN101537351B - Catalyst for catalytic combustion - Google Patents
Catalyst for catalytic combustion Download PDFInfo
- Publication number
- CN101537351B CN101537351B CN 200810102403 CN200810102403A CN101537351B CN 101537351 B CN101537351 B CN 101537351B CN 200810102403 CN200810102403 CN 200810102403 CN 200810102403 A CN200810102403 A CN 200810102403A CN 101537351 B CN101537351 B CN 101537351B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- weight
- metal
- earth metal
- rare earth
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 62
- 238000007084 catalytic combustion reaction Methods 0.000 title claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 21
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 18
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 16
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 14
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 13
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 13
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 12
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000011572 manganese Substances 0.000 claims abstract description 6
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- 239000010949 copper Substances 0.000 claims abstract description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000010936 titanium Substances 0.000 claims abstract description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000010941 cobalt Substances 0.000 claims abstract description 3
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 3
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 3
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 3
- 239000011701 zinc Substances 0.000 claims abstract description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 29
- 238000002485 combustion reaction Methods 0.000 abstract description 13
- 239000003345 natural gas Substances 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 230000004913 activation Effects 0.000 description 4
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 239000002250 absorbent Substances 0.000 description 3
- 230000002745 absorbent Effects 0.000 description 3
- 230000001476 alcoholic effect Effects 0.000 description 3
- 239000003610 charcoal Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 description 3
- 239000011565 manganese chloride Substances 0.000 description 3
- 229940099607 manganese chloride Drugs 0.000 description 3
- 235000002867 manganese chloride Nutrition 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- IPCAPQRVQMIMAN-UHFFFAOYSA-L zirconyl chloride Chemical compound Cl[Zr](Cl)=O IPCAPQRVQMIMAN-UHFFFAOYSA-L 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000001802 infusion Methods 0.000 description 2
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 2
- 229940078494 nickel acetate Drugs 0.000 description 2
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 240000007049 Juglans regia Species 0.000 description 1
- 235000009496 Juglans regia Nutrition 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 235000009827 Prunus armeniaca Nutrition 0.000 description 1
- 244000018633 Prunus armeniaca Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000004247 glycine and its sodium salt Substances 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000011020 pilot scale process Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical class CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- -1 tetrabutyl titanate ester Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 235000020234 walnut Nutrition 0.000 description 1
Landscapes
- Catalysts (AREA)
Abstract
The invention discloses a catalyst for catalytic combustion, which is characterized by comprising a catalytic component and a carrier component, wherein the catalytic component comprises an alkaline-earth metal, rare earth metals, a subgroup metal and zirconia; according to 100 weight portions of zirconia, the weight portion of the alkaline-earth metal is 2 to 40, the weight portion of the rare earth metals is 6 to 30, and the weight portion of the subgroup metal is 1 to 30; the rare earth metals are lanthanum and cerium in a weight ratio of (3-20):1; the subgroup metal is one selected from titanium, iron, cobalt, nickel, zinc, manganese and copper; and the carrier is active carbon accounting for 60 to 98 percent of the weight of the catalyst. Compared with the prior art, the catalyst has the characteristics of low cost, low temperature for completely converting natural gas and low discharge amount of CO and NOx after combustion.
Description
Technical field
The invention relates to a kind of combustion catalyst, more specifically say about a kind of catalyst for combustion of natural gas.
Background technology
Natural gas (CH
4) low than fuel contamination degree such as oil, coals, the CO that in combustion process, discharges
2, SO
2And NO
xLess Deng pollutant, catalytic combustion is further control and eliminates NO
xEffective ways.Compare with the ordinary combustion mode, catalytic combustion has higher efficiency of combustion and capacity usage ratio.
Catalytic combustion is compared with traditional flame combustion, and following advantage is arranged: 1) initiation temperature (transform 10% temperature) is low, less energy consumption, and flameholding, even reach and need not extraneous the heat transfer behind the initiation temperature and just can finish oxidation reaction; 2) purification efficiency is high. pollutant (NOX and imperfect combustion product etc.) emission level is low, and general organic exhaust gas conversion ratio is all more than 98%. can reduce in a large number the generation of NOX gas under the initiation temperature. behind the CC-20 type methane catalytic combustion catalyst reaction of Lanzhou Chemical Physics research institute of Chinese Academy of Sciences catalysis pilot scale chamber development in the tail gas methane volume fraction be less than 5 * 10-6; 3) adaptation oxygen concentration scope is large, non-secondary pollution, and burning mitigation, and running expense is few, convenient operation and management; 4) noise is low.
Greatest difficulty in the catalytic combustion technology is exactly to select suitable catalyst at present.Catalyst for catalytic combustion mainly contains carried noble metal, Ca-Ti ore type and hexa-aluminate type catalyst.
Carried noble metal type catalyst has good complete oxidation activity and good stability, and Pt, Pd are common noble metals.At high temperature volatile, the sintering of noble metal and poisoning and expensive price itself make its application in the methane high-temp combustion be subject to certain limitation, usually will it is in the majority for the low temperature ignition stage of burner.ABO3 perovskite composite oxides, hexa-aluminate type catalyst are commonly referred to as non-metallic catalyst, and perovskite catalyst is when applied at elevated temperature, and the phenomenon that also exists high temperature sintering that specific area is reduced has a negative impact to activity.Loaded noble metal catalyst and perovskite type catalyst are fit to the low thermophase of methyl hydride combustion, and non-precious metal catalyst then is fit to the methane high temperature catalytic combustion.
CN1224047A discloses a kind of Catalysts and its preparation method for combustion of natural gas, and catalyst consists of (percentage by weight): subgroup metal 2-20%, alkaline-earth metal 0.5-15%, lanthanide series metal 0-15%, ZrO
255-95%.The service condition of catalyst is reaction temperature 390-800 ℃, and air speed 18000-36000ml/g.h is used for the natural gas burning in 50ppm-20% natural gas/air Mixture, can make hydrocarbon content in the combustion tail gas less than 1ppm, makes simultaneously CO and NO
xContent less than 1ppm.
Summary of the invention
The objective of the invention is on the basis of existing technology, for the deficiencies in the prior art, provide CO after the low and burning of a kind of cost temperature relatively low, that natural gas 100% is transformed, By Non-precious Metal Catalysts combustion catalyst that the NOx discharge capacity is low.
Catalyst for catalytic combustion provided by the invention, it is characterized in that being formed by catalyst component and carrier, said catalyst component is alkaline-earth metal, rare earth metal, subgroup metal and zirconia, take zirconia as 100 parts of weight as benchmark, alkaline-earth metal is 2-40 part, rare earth metal is 6-30 part, the subgroup metal is 1-30 part, rare earth metal is selected from lanthanum and cerium, the weight ratio of lanthanum and cerium (3-20): 1, subgroup element is selected from a kind of in titanium, iron, cobalt, nickel, zinc, manganese and the copper, and said carrier is active carbon, counts 60-98% with catalyst weight.
Catalyst provided by the invention, cost is low than noble metal catalyst, ignition better performances at low temperatures, and CO after the burning, NOx discharge capacity are low.
The specific embodiment
Catalyst provided by the invention, it preferably forms take zirconia as 100 parts of weight as benchmark, and alkaline-earth metal is 5-25 part, and rare earth metal is 2-15 part, and subgroup element is 2-15 part.
In the catalyst provided by the invention, wherein said alkaline-earth metal is preferably magnesium, and said subgroup element is preferred manganese or copper.
Although in the catalyst for catalytic oxidation, contain certain rare earth element and can increase catalyst activity stability at high temperature, but the inventor finds by a large amount of tests, if in catalyst, contain simultaneously two kinds of rare earth elements of lanthanum and cerium, when the content of particularly controlling lanthanum in the two the proportioning is far longer than the content of cerium, low temperature ignition performance for catalyst has beyond thought help, and the weight ratio of preferred lanthanum and cerium is (4-15): 1, more preferably (7-13): 1.
In the catalyst provided by the invention, said carrier is active carbon, and weight is preferably 75-90%.Said active carbon is preferably powdery shell class active carbon, and preferably with coconut husk, walnut shell or the apricot shell class active carbon of gas activation method or the preparation of KOH medicine activation method, preferred specific area is 700-3000m
2/ g, granularity are less than 200 microns.
Catalyst provided by the invention, that powdery shell class active carbon is carried out the acid treatment ash disposal, after oxidation processes is removed surface reduction functional group, then form content by catalyst the predecessor of zirconium is dissolved in the solution that is made into 0.02-0.5ml/L concentration in the ethanol, absorbent charcoal carrier after the impregnation process, again concentration is the alkaline-earth metal predecessor of 0.02-0.5ml/L after the oven dry, the rare earth metal predecessor, the alcoholic solution of subgroup element predecessor is order dipping or hybrid infusion respectively, again with hydrogen, in potassium borohydride or the hydrazine hydrate one or more reduce to process and obtain.
The preparation process that illustrates in more detail catalyst of the present invention is as follows:
Active carbon concentration is that the aqueous hydrochloric acid solution of 10-20 % by weight is added a cover in water-bath and boiled at least 0.5 hour, removes soluble impurity, ash and the aperture tamper on surface, and is neutral to filtrate with deionized water drip washing, filters post-drying; Be that the salpeter solution of 10-20 % by weight carried out oxidation processes at least 0.5 hour at normal temperatures with the active carbon concentration after the impurity elimination, then use deionized water drip washing neutral to filtrate, oven dry adds deionized water and makes active carbon suspension; Under the condition that stirs, the predecessor that adds the zirconium of 0.02-0.5ml/L concentration in the above-mentioned active carbon suspension, such as zirconyl chloride, zirconyl nitrate, tetraalkyl zirconate etc., again concentration is the alkaline-earth metal predecessor of 0.02-0.5ml/L after the oven dry, the rare earth metal predecessor, the alcoholic solution of subgroup element predecessor, magnesium chloride for example, barium nitrate, cerous nitrate, lanthanum nitrate, nickel acetate, cobalt nitrate, manganese chloride, copper nitrate, ferric nitrate, the alcoholic solution of tetraalkyl titanate flood respectively or the above-mentioned load of hybrid infusion the absorbent charcoal carrier of zirconium, after under 10-30 ℃ of lower the stirring 2-48 hour, dropping concentration is that the NaOH solution adjustment pH value of 5 % by weight is 8-10 ageing 2-10 hour; Keep system temperature to pass into the hydrogen that flow is 30ml/min to suspension under 25-30 ℃, or slow adding 10mL concentration is the sodium borohydride solution of 5 % by weight simultaneously, under agitation reduction activation at least 1 hour is washed to Cl with deionized water after filtering
-Concentration is less than 10
-6Then M is 1.013 * 10 at 100-120 ℃, vacuum
-3-1.013 * 10
-4Under the condition of Pa dry 4-20 hour, the preservation of under nitrogen protection, coming out of the stove.
The present invention is further illustrated below by embodiment and Comparative Examples, but content not thereby limiting the invention.
In an embodiment, said active carbon is for analyzing pure commodity (specific surface 860m
2/ g, moisture content 10%, the pH value is 3.5, granularity be the 40-60 micron account for 50%, all the other are the 60-160 micron).
Used zirconyl nitrate, zirconyl chloride, tetrabutyl titanate ester, magnesium chloride, barium nitrate, cerous nitrate, lanthanum nitrate, nickel acetate, cobalt nitrate, manganese chloride, copper nitrate, ferric nitrate, tetrapropyl titanate esters etc. are chemical pure among the embodiment.
Embodiment 1
Active carbon carrier as catalyst after following preliminary treatment uses.
Active carbon is that the aqueous hydrochloric acid solution of 10 % by weight is added a cover in water-bath and boiled 6 hours with 500ml concentration, removes soluble impurity, ash and the aperture tamper on surface, and is neutral to filtrate with deionized water drip washing, after filtering in 110 ℃ of oven dry; Be that the salpeter solution of 20 % by weight carried out oxidation processes 6 hours at normal temperatures with the active carbon after the impurity elimination with 150ml concentration, then use deionized water drip washing neutral to filtrate, 110 ℃ of oven dry.Add the 100mL deionized water and make active carbon suspension.
Under the condition that stirs, add concentration in the above-mentioned active carbon suspension and be respectively zirconyl chloride, the magnesium chloride of 22.5g/l, 2.5g/l, the aqueous solution of manganese chloride, constant temperature absorption is after 2-48 hour under 30 ℃ and strong stirring, drips 20mL concentration and be the NaOH ageing of solution 10 hours of 5 (weight) %.
Pass into the hydrogen that flow is 30ml/min to suspension under 30 ℃, slowly adding 10mL concentration simultaneously is sodium borohydride (Chinese Medicine Solution on Chemical Reagents in Shanghai station the is analyzed pure) solution of 5 % by weight, under agitation reduction activation 4 hours.Wash to Cl with deionized water after filtering
-Concentration is less than 10
-6Then M is 1.013 * 10 at 110 ℃, vacuum
-3-1.013 * 10
-4Carried out drying under the condition of Pa 4 hours, the preservation of under nitrogen protection, coming out of the stove.
In the prepared catalyst, the weight of active carbon is 85%, and zirconia is that 100 parts of weight are the benchmark meter in the catalyst component, and magnesium is 10 parts, rare earth metal is 6 parts, and manganese is 3 parts, and said rare earth metal is selected from lanthanum and cerium, the weight ratio of lanthanum and cerium 4: 1, it is numbered catalyst A, lists in table 1.
Embodiment 2-10
Preparation process is with embodiment 1, adjusts the content in the wherein absorbent charcoal carrier and catalyst component, obtains respectively catalyst B, C, D, E, F, G, H, I, J, and see Table 1 its concrete composition.
Comparative Examples 1,2
This Comparative Examples explanation is with single rare-earth elements of lanthanum or the catalyst of cerium, and numbering is respectively W1, W2.Form and list in the table 1.
Comparative Examples 3,4
This Comparative Examples explanation is numbered and is respectively W3, W4 when the catalyst that the ratio of rare-earth elements of lanthanum and cerium is different from when of the present invention.Form and list in the table 1.
Table 1
Embodiment 11
The reaction effect of catalyst A-J of embodiment of the invention 1-10 is described.
Reaction condition: 1% natural gas/air Mixture, gas space velocity is counted 20000ml/gh take the catalyst component weight in the catalyst as benchmark, and the concentration of CO, NOx the results are shown in Table 2 in the temperature that investigation natural gas 100% transforms, the tail gas.
Comparative Examples 5
The reaction effect of this Comparative Examples explanation comparative catalyst W1-W4.
Condition the results are shown in table 2 with embodiment 11.
Table 2
| The catalyst numbering | The temperature that natural gas 100% transforms (℃) | The concentration of CO, NOx in the tail gas |
| A | 550 | Less than 1PPM |
| B | 600 | Less than 1PPM |
| C | 575 | Less than 1PPM |
| D | 650 | Less than 1PPM |
| E | 640 | Less than 1PPM |
| F | 550 | Less than 1PPM |
| G | 580 | Less than 1PPM |
| H | 595 | Less than 1PPM |
| I | 610 | Less than 1PPM |
| J | 600 | Less than 1PPM |
| W1 | 790 | Less than 1PPM |
| W2 | 800 | Less than 1PPM |
| W3 | 850 | Less than 1PPM |
| W4 | 820 | Less than 1PPM |
From the results shown in Table 2, with respect to the comparative catalyst, the low temperature ignition performance of catalyst provided by the invention is better.
Claims (5)
1. catalyst for catalytic combustion, it is characterized in that being formed by catalyst component and carrier, said catalyst component is alkaline-earth metal, rare earth metal, subgroup metal and zirconia, take zirconia as 100 parts of weight as benchmark, alkaline-earth metal is 2-40 part, rare earth metal is 6-30 part, the subgroup metal is 1-30 part, rare earth metal is selected from lanthanum and cerium, the weight ratio of lanthanum and cerium (4-15): 1, the subgroup metal is selected from a kind of in titanium, iron, cobalt, nickel, zinc, manganese and the copper, and said carrier is active carbon, counts 60-98% with catalyst weight.
2. according to the catalyst of claim 1, wherein, the weight ratio of lanthanum and cerium is (7-13): 1.
3. according to the catalyst of claim 1, wherein said alkaline-earth metal is magnesium, and said subgroup metal is manganese or copper.
4. according to the catalyst of claim 1, wherein said active carbon is counted 75-90% with catalyst weight.
5. according to the catalyst of claim 1 or 4, said active carbon specific area is 700-3000m
2/ g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200810102403 CN101537351B (en) | 2008-03-21 | 2008-03-21 | Catalyst for catalytic combustion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200810102403 CN101537351B (en) | 2008-03-21 | 2008-03-21 | Catalyst for catalytic combustion |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101537351A CN101537351A (en) | 2009-09-23 |
| CN101537351B true CN101537351B (en) | 2013-03-27 |
Family
ID=41120872
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200810102403 Expired - Fee Related CN101537351B (en) | 2008-03-21 | 2008-03-21 | Catalyst for catalytic combustion |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101537351B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102059093B (en) * | 2009-11-18 | 2012-10-10 | 中国科学院生态环境研究中心 | Arsenic and fluorine removing nano-composite adsorbent |
| CN102261677A (en) * | 2011-05-25 | 2011-11-30 | 浙江工业大学 | Efficient energy-saving environmentally-friendly cooking range |
| CN103111303A (en) * | 2013-01-16 | 2013-05-22 | 济南迪诺环保科技有限公司 | Complete combustion catalyst for natural gas, coal bed methane and liquefied gas |
| CN104293411B (en) * | 2014-09-10 | 2016-06-22 | 济南大学 | Preparation method of coal combustion catalyst |
| CN114682221B (en) * | 2022-06-01 | 2022-08-16 | 矿冶科技集团有限公司 | Selective adsorption material for treating lead and cadmium-containing wastewater, preparation method thereof and method for treating lead and cadmium-containing wastewater by using selective adsorption material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1224047A (en) * | 1998-01-23 | 1999-07-28 | 中国科学院山西煤炭化学研究所 | Catalyst for combustion of natural gas and preparing process thereof |
| CN1509813A (en) * | 2002-12-20 | 2004-07-07 | 中国科学院生态环境研究中心 | Oxygen-enriched tail gas nitrogen oxide purification catalyst |
| CN101143325A (en) * | 2006-09-13 | 2008-03-19 | 中国科学院大连化学物理研究所 | A kind of method for preparing catalyst and its application |
-
2008
- 2008-03-21 CN CN 200810102403 patent/CN101537351B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1224047A (en) * | 1998-01-23 | 1999-07-28 | 中国科学院山西煤炭化学研究所 | Catalyst for combustion of natural gas and preparing process thereof |
| CN1509813A (en) * | 2002-12-20 | 2004-07-07 | 中国科学院生态环境研究中心 | Oxygen-enriched tail gas nitrogen oxide purification catalyst |
| CN101143325A (en) * | 2006-09-13 | 2008-03-19 | 中国科学院大连化学物理研究所 | A kind of method for preparing catalyst and its application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101537351A (en) | 2009-09-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6645439B2 (en) | Exhaust gas clean-up catalyst | |
| EP2301661B1 (en) | Honeycomb catalyst for purifying exhaust gas discharged from automobile, method for producing the same, and exhaust gas purifying method using the catalyst | |
| EP1837076B1 (en) | Diesel particulate filter catalyst with low no2 emissions | |
| US20080141660A1 (en) | Catalyst And System For Reducing Exhaust Of Diesel Engines | |
| CN101537351B (en) | Catalyst for catalytic combustion | |
| CN102059127B (en) | Catalyst for CO normal temperature catalytic oxidation and preparation method thereof | |
| CN103191733A (en) | Low-concentration methane combustion catalyst and its preparation method | |
| JP6053811B2 (en) | Supported noble metal catalysts for exhaust gas treatment | |
| RU2635092C2 (en) | Catalytic composition | |
| CN101722010B (en) | Novel nitrogen oxide storage and reduction catalyst for exhaust gas purification of lean burn gasoline engine or diesel engine | |
| US6767526B1 (en) | Method for treating by combustion carbon-containing particles in an internal combustion engine exhaust circuit | |
| CN101474559A (en) | Catalyst for purifying exhaust of petrol engine using ethyl hydrate as fuel and preparation method thereof | |
| CN111054374A (en) | Catalytic combustion catalyst for PTA oxidized tail gas and application thereof | |
| Ogugua et al. | Advancements in low-temperature NH3-SCR of NOx using Ba-based catalysts: a critical review of preparation, mechanisms, and challenges | |
| CN1504260A (en) | Integral gas combustion catalyst and preparation method thereof | |
| CN103170348A (en) | Silver-containing normal-temperature monolithic catalyst for carbon monoxide and preparation method thereof | |
| CN111349481A (en) | Environment-friendly automobile exhaust cleaning agent and preparation method thereof | |
| CN114950466B (en) | A kind of non-noble metal catalyst and its preparation method and application | |
| CN102068987A (en) | Rare earth modified activated carbon-supported nanogold catalytic material and preparation method thereof | |
| CN115518631A (en) | A kind of NOx adsorption-selective catalytic reduction catalyst and its preparation method and application | |
| CN101642715B (en) | Pyrophosphate catalyst of cerium for selectively catalyzing and reducing nitrogen oxides and preparation method thereof | |
| US20160214095A1 (en) | Oxidation catalyst for exhaust gas purification, catalyst structure for exhaust gas purification, and method for purifying exhaust gas using catalyst structure | |
| JP4503314B2 (en) | Exhaust gas purification catalyst | |
| CN114950422B (en) | Methane oxidation catalyst and preparation method and application thereof | |
| CN116099569B (en) | A catalyst for purifying exhaust gas of an ammonia internal combustion engine and its preparation method and use |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C53 | Correction of patent for invention or patent application | ||
| CB03 | Change of inventor or designer information |
Inventor after: Zhao Ran Inventor after: Zhao Xu Inventor after: Zhao Yongjun Inventor after: Duo Wen Inventor after: Zhao Xin Inventor after: Yin Dongyuan Inventor before: Zhao Yongjun Inventor before: Duo Wen Inventor before: Zhao Xin |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: INVENTOR; FROM: ZHAO YONGJUN DUO WEN ZHAO XIN TO: ZHAO RAN ZHAO XU ZHAO YONGJUN DUO WEN ZHAO XIN YIN DONGYUAN |
|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130327 Termination date: 20140321 |