CN1302686A - Deoxidizing agent of molybdenum oxide and its preparing process - Google Patents
Deoxidizing agent of molybdenum oxide and its preparing process Download PDFInfo
- Publication number
- CN1302686A CN1302686A CN 01105111 CN01105111A CN1302686A CN 1302686 A CN1302686 A CN 1302686A CN 01105111 CN01105111 CN 01105111 CN 01105111 A CN01105111 A CN 01105111A CN 1302686 A CN1302686 A CN 1302686A
- Authority
- CN
- China
- Prior art keywords
- deoxidizer
- active component
- preparation
- carrier
- deoxidation
- 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.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 6
- 229910000476 molybdenum oxide Inorganic materials 0.000 title claims description 12
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 title claims description 12
- 239000003795 chemical substances by application Substances 0.000 title description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 33
- 238000002360 preparation method Methods 0.000 claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000001301 oxygen Substances 0.000 claims abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 12
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000001257 hydrogen Substances 0.000 claims abstract description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 7
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 6
- 230000004913 activation Effects 0.000 claims abstract description 5
- 238000005470 impregnation Methods 0.000 claims abstract description 5
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 5
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 4
- 239000010941 cobalt Substances 0.000 claims abstract description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052742 iron Inorganic materials 0.000 claims abstract description 4
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 4
- 239000010937 tungsten Substances 0.000 claims abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 4
- 239000011149 active material Substances 0.000 claims description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 2
- 229940010552 ammonium molybdate Drugs 0.000 claims description 2
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 2
- 239000011609 ammonium molybdate Substances 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims 1
- 239000004480 active ingredient Substances 0.000 claims 1
- 239000013543 active substance Substances 0.000 claims 1
- 239000000969 carrier Substances 0.000 claims 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims 1
- 239000007789 gas Substances 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 15
- 229910052750 molybdenum Inorganic materials 0.000 abstract description 9
- 239000011733 molybdenum Substances 0.000 abstract description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052717 sulfur Inorganic materials 0.000 abstract description 4
- 239000011593 sulfur Substances 0.000 abstract description 4
- 150000002751 molybdenum Chemical class 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 239000000470 constituent Substances 0.000 description 9
- 238000006356 dehydrogenation reaction Methods 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000007493 shaping process Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000008030 elimination Effects 0.000 description 3
- 238000003379 elimination reaction Methods 0.000 description 3
- 239000008246 gaseous mixture Substances 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 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 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 150000003658 tungsten compounds Chemical class 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910003310 Ni-Al Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910018487 Ni—Cr Inorganic materials 0.000 description 1
- 241001074085 Scophthalmus aquosus Species 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001785 cerium compounds Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical compound [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- 238000002803 maceration Methods 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- -1 metallurgy Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000005078 molybdenum compound Substances 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000012629 purifying agent Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
Landscapes
- Catalysts (AREA)
Abstract
本发明公开了一种高效多功能钼系脱氧剂及其制备方法。所发明脱氧剂的活性组份为由钼、钨、钴、铁、镍、氧等元素构成的组合物,其中钼含量宜在5—45%(wt)范围内选取。其制备方法采用浸渍法制备,包括催化剂载体制备,活性组份均相液配制、活性组分的浸渍,还原活化处理四个步骤。按照本发明的制备方法得到的脱氧剂,可广泛用于含氢和不含氢气氛中使用,也可用于含硫气体中使用,具有活性高、处理量大、成本低、残氧量低(0.1ppm)等特点。The invention discloses an efficient and multifunctional molybdenum series deoxidizer and a preparation method thereof. The active component of the invented deoxidizer is a composition composed of molybdenum, tungsten, cobalt, iron, nickel, oxygen and other elements, wherein the content of molybdenum is preferably selected within the range of 5-45% (wt). The preparation method adopts the impregnation method, including four steps of catalyst carrier preparation, active component homogeneous liquid preparation, active component impregnation, and reduction and activation treatment. The deoxidizer obtained according to the preparation method of the present invention can be widely used in hydrogen-containing and hydrogen-free atmospheres, and can also be used in sulfur-containing gases, and has high activity, large processing capacity, low cost, and low residual oxygen ( 0.1ppm) and other characteristics.
Description
The present invention relates to a kind of deoxidizing agent of molybdenum oxide, particularly a kind of can deoxidation in hydrogeneous and not hydrogeneous atmosphere, also can contain the deoxidizing agent of molybdenum oxide of deoxidation in the gaseous mixture of carbon monoxide at sulfur-bearing.
Along with the development of industries such as electronics, building materials, metallurgy, chemical industry, more and more higher to the requirement of the quality of high-purity gas and quantity.In order to produce high-purity gas, industrial cryogenic rectification method, low-temperature adsorption, film diffusive separation method and catalysis absorption method etc. of having developed in succession at present, wherein catalysis absorption method is the most commonly used.In of the requirement of many industries to high-purity gas, oxygen content is had higher requirements, its remaining oxygen is in the ppm level, even ppb level, owing to adopt the deoxidier deoxidation, have that equipment is simple, easy to operate, treating capacity is big, deoxidation effect good, low power consumption and other advantages, obtained in recent years using widely.Magazines such as special gas in recent years, low temperature and special gas have been introduced domestic some kinds of comparatively ripe deoxidiers, as: 1) copper deoxidier is representative with 0603 type deoxidier mainly, at temperature 180-240 ℃, and air speed 1000-3000h
-1Condition under, can be with general hydrogen, general nitrogen deoxidation to 10ppm, i.e. the deoxidation degree of depth can reach 10ppm, deoxidizing capacity can reach 10 (ml O
2)/(g deoxidier).2) silver-colored deoxidier is representative with 201 type AgX type gas purifying agents mainly, at normal temperature, and air speed＜10000h
-1Condition under, can be with the mist deoxidation to 1ppm, i.e. the deoxidation degree of depth can reach 1ppm, deoxidizing capacity can reach 10ml O
2/ (g deoxidier).3) palladium deoxidier, the kind of such deoxidier is more, and deoxidation effect is better, can reach below the 1ppm.4) the nickel deoxidier mainly contains Ni-Cr
2O
3System and Ni-Al
2O
3System, cheap, but deoxidation effect is relatively poor.5) manganese series catalyzer, main 401,402,401-B type, in room temperature, air speed 10000h
-1Condition under, can have good deoxidation effect with the gas deoxidation to 0.1ppm.
Although manganese deoxidier has good deoxidation effect.But this deoxidier is very unstable, in case be exposed in the air, then emit a large amount of heat, lost efficacy immediately, so should not store and transport, only suitable now-making-now-using, thereby limited its suitability for industrialized production, present industrial deoxidier, inexpensive person's poor-performing, function admirable person costs an arm and a leg, and in addition, above-mentioned various deoxidiers run into and contain H
2S, COS sulfides, and when containing the gas of impurity such as CO, all very easy poisoning is so its scope of application has been subjected to very big restriction.In addition, manganese deoxidier also is not suitable for and contains H
2The deoxidation treatment of foreign gases such as S, COS, CO.Developed HC-1 type dehydrogenation catalyst in recent years and there are the problems referred to above equally in the PtS dehydrogenation catalyst.
The preparation that a kind of molybdenum is a dehydrogenation catalyst is disclosed among the Chinese patent ZL 93 1 12631.2, but the catalyst for preparing in this patent, mainly be sulfide, in use there is a small amount of sulphur to emit, the industry that influences this catalyst is promoted, the zirconium compounds of being introduced or the effect of cerium compound are little, and the oxide catalyst of its preparation exists that serviceability temperature is higher, the life-span is short and the more high deficiency of price.
The objective of the invention is to overcome the above-mentioned shortcoming of existing deoxidier, by prescription screening, preparation condition and formulation optimization, provide that a kind of catalyst activity constituent content is little, impurity poisoning such as preparation technology is simple, price is cheaper, productions is easy, deoxidation effect is good, resisting sulfide and carbon monoxide and do not have the high-efficiency multi-function deoxidizing agent of molybdenum oxide of suitability for industrialized production in a large number of the stable storage of sulphur effusion, and the preparation method of described deoxidier.
Realize the technical scheme of the object of the invention:
The said deoxidizing agent of molybdenum oxide of the present invention system is made of carrier and deoxy activity master component and helper component.
Said carrier can be γ-Al
2O
3, SiO
2, TiO
2, active carbon, or their mixture;
Said deoxy activity component is the composition that various elements such as molybdenum, tungsten, iron, cobalt, nickel, oxygen constitute, available following general formula:
MoOaAObDOc is wherein: Mo-is a molybdenum element; A-is tungsten or cobalt element and composition thereof; D-is iron or nickel element and composition thereof; A=1.0,1.5,2.0,2.5; B=1.0,1.5,2.0,2.5; C=1.0,1.5,2;
In the deoxidier, the percentage by weight ratio of components scope of deoxy activity component is: Mo:5-45% (wt); A:0.1-20% (wt); D:0-6% (wt); O:20-40%;
Wherein: the amount of oxygen is chosen and must be complementary by forming required metal oxide.
The weight percent content of suitable deoxy activity component is 5-45%, and is preferred 15～35%, and all the other are carrier.
In the molybdenum deoxidier, introduce tungsten compound or/and cobalt compound, or/and the cooperative effect of cobalt molybdenum compound, improve the deoxidizing capacity of molybdenum deoxidier by the tungsten compound; In the molybdenum deoxidier, introduce iron compound or/and nickel compound, can improve the activity of molybdenum deoxidier, the reaction temperature when reducing deoxidation.
The preparation method of molybdenum series catalyst of the present invention mainly comprises the steps:
1) the suitable catalyst carrier of preparation; 2) homogeneous phase solution of preparation dehydrogenation catalyst active constituent; 3) dipping of active constituent; 4) reduction activation heat treatment.
1) preparation of catalyst carrier:
According to the different operating positions and the raw-material situation of this catalyst, select γ-Al
2O
3, SiO
2, active carbon or TiO
2Deng the preparation shaping carrier, the specific area that requires carrier is at 100-300m
2/ g, pore size are at 0.5～0.7nm, and pore volume is more than 0.4ml/g, and compression strength is not less than the 60N/ grain, also can buy corresponding carrier as required;
2) preparation of active constituent:
According to proportioning take by weighing active material (as ammonium molybdate, ammonium tungstate, nitric acid brill, ferric nitrate etc.) respectively or mixed dissolution in water, make homogeneous phase solution, remove by filter insoluble matter, add the pH=9-11 of ammoniacal liquor regulator solution, the maceration extract of active constituent;
3) dipping of active constituent:
Under stirring condition, the carrier for preparing is placed the active constituent solution for preparing respectively, also can adopt equivalent impregnation, being about to active constituent solution is sprayed on the carrier equably, suitable 14-16 hour of dip time, temperature is between 40-70 ℃, promptly get the catalyst of supported active component, be placed on earlier in the vacuum drying oven, in 100-120 ℃, under vacuum 80～100mmHg dry 9-10 hour, roasting in Muffle furnace then, sintering temperature is 350-550 ℃, and roasting time is 8-10 hour, and getting the oxidized form molybdenum is mixture catalyzer;
4) reduction activation is handled:
Oxidation catalyst with above-mentioned preparation places reduction furnace, reduces 8-12 hour in pure hydrogen, and by certain formula heating reduction, reduction temperature is 250-500 ℃, and after reduction finished, nitrogen replacement 2-3 hour used in cooling, promptly obtains highly active molybdenum series catalyst.
Obtain high-efficiency multi-function molybdenum oxide dehydrogenation catalyst according to above-mentioned prescription and preparation method, can be used for the deoxidation of general nitrogen, general hydrogen, synthesis gas, argon gas, alkanes gaseous mixture and sulfurous gas, its deoxidation degree of depth can reach 0.1ppm, its effect such as table 1:
| Sequence number | Handle object | Working condition | Can reach the deoxidation degree of depth |
| ????1 | General hydrogen deoxidation | Normal pressure; 100～250 ℃, air speed 6000-10000h -1H 2:98％(V/V),O 2: 0.5% (V/V) other: 1.5% (V/V) | ????0.1ppm |
| ????2 | General nitrogen deoxidation | Normal pressure～6atm; Normal temperature, air speed: 1000-3000h -1N 2:99％(V/V),O 2: 0.4% (v/v) adsorbs deoxidation | 0.1ppm maximal oxygen uptake 106ml/g |
| ????3 | General nitrogen deoxidation | Normal pressure; 100 ℃, 100～250 ℃, air speed is 3000～10000h -1N 2:95％(v/v),H 2: the deoxidation of 3% (v/v) 02:0.5% (v/v) catalyst | ????0.1ppm |
| ????4 | Sulfur-bearing, contain CO gaseous mixture such as synthetic gas deoxidizing | 20atm; Temperature＞100 ℃, H 2:48％(V/V),CO:51％ ??(V/V) H 2The deoxidation of S:0.11% (V/V) catalyst | ????0.1ppm |
Table 1
By table 1 as seen, the high-efficiency multi-function molybdenum oxide dehydrogenation catalyst that the present invention prepares, its deoxidation degree of depth can reach 0.1ppm, can be used in catalytic deoxidation in the hydrogeneous gas, its deoxidation degree of depth also reaches precious metals palladium catalyst, but price be its 1/2～1/3, also can be used in the sulfur-bearing atmosphere and use.
Use in industry to facts have proved that this catalyst has active constituent height, long service life, advantage such as can reach more than 2 years, cost is low, disposal ability is big.
This catalyst can also be used in deoxidation in the gas that does not allow hydrogeneous atmosphere, the experiment proved that, its deoxidizing capacity can reach 106 (ml.O
2)/g (deoxidier) for existing more than 4 times of commercial catalyst, has the wide industrial application prospect.
Embodiment 1
With 30g (NH
4)
4Mo
7O
246H
2O, 12g, (NH
4)
5H
5[H
2(WO
4)] 6H
2O mixes and to be dissolved in the 50g water, crosses the elimination insoluble matter, and regulating the pH value with ammoniacal liquor is 10, with spray solution at 50gAl
2O
3On the carrier (purchase shaping carrier), being 50 ℃ in temperature flooded 14 hours down, at 120 ℃, vacuum is under the 100mmHg dry 9 hours, roasting in muffle furnace then 400 ℃ of following roastings 6 hours, is warmed up to 540 ℃ of roastings 3 hours again, used hydrogen reducing at last 10 hours, reduction temperature is 280 ℃, with the nitrogen cooling, promptly gets the said deoxidizing agent of molybdenum oxide of the present invention.
This catalyst is to general nitrogen hydrogenation (N
2: 95% (v/v), H
2: 3% (v/v), O
2: 0.5% (v/v)) carrying out deoxidation, is 100 ℃ in 1atm, temperature, and air speed is 6000～10000h
-1Condition, remaining oxygen is 0.1ppm.Embodiment 2
Remove the carrier of catalyst and select TiO for use
2Outward, the preparation of dehydrogenation catalyst is with embodiment 1.
This catalyst is to general nitrogen (N
2: 99% (v/v) O
2: 0.5% (v/v)) adsorb deoxidation, at 1atm, normal temperature, air speed is 1000～3000h
-1Under the condition, remaining oxygen is 0.1ppm, and maximal absorptive capacity is 106ml/g, saturated after, logical hydrogen is at 200 ℃ of regeneration 3 hours down, activation recovering.Embodiment 3
With 25g (NH
4)
4Mo
7O
246H
2O25g, 10g (NH
4)
5H
5[H
2(WO
4)] 6H
2O, 7gCo (NO
3)
3, 3g Fe (NO
3)
3, mix and to be dissolved in the 50g water, cross the elimination insoluble matter, regulating the pH value with ammoniacal liquor is 11, with spray solution at 50g Al
2O
3On the carrier (purchase shaping carrier), being 60 ℃ in temperature flooded 15 hours down, at 120 ℃, vacuum is under the 100mmHg dry 9 hours, roasting in muffle furnace then, 550 ℃ of following roastings 8 hours, used hydrogen reducing at last 10 hours, reduction temperature is 280 ℃, with the nitrogen cooling, promptly get the said deoxidizing agent of molybdenum oxide of the present invention.
This catalyst adds sulphur (H to general hydrogen
2: 97% (v/v), H
2S:0.1% (v/v), O
2: 0.5% (v/v)) carrying out deoxidation, is 100 ℃ in 3atm, temperature, and air speed is 6000～10000h
-1Condition under, remaining oxygen is 0.1ppm.Embodiment 4
With 30g (NH
4)
4Mo
7O
246H
2O25g, 7g (NH
4)
5H
5[H
2(WO
4)] 6H
2O, 3gCo (NO
3)
3, 3g Fe (NO
3)
3, 3g Ni (NO
3)
2Mix and to be dissolved in the 50g water, cross the elimination insoluble matter, regulating the pH value with ammoniacal liquor is 10, with spray solution at 50g Al
2O
3On the carrier (purchase shaping carrier), being 60 ℃ in temperature flooded 15 hours down, at 120 ℃, vacuum is under the 100mmHg dry 9 hours, roasting in muffle furnace then, 550 ℃ of following roastings 8 hours, used hydrogen reducing at last 10 hours, reduction temperature is 280 ℃, with the nitrogen cooling, promptly get the said deoxidizing agent of molybdenum oxide of the present invention.
This catalyst adds sulphur (H to general hydrogen
2: 97% (v/v), H
2S:0.1% (v/v), O
2: 0.5% (v/v)) carrying out deoxidation, is 100 ℃ in 1atm, temperature, and air speed is 6000～10000h
-1Condition under, remaining oxygen is 0.1ppm.
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01105111 CN1111082C (en) | 2001-01-09 | 2001-01-09 | Deoxidizing agent of molybdenum oxide and its preparing process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01105111 CN1111082C (en) | 2001-01-09 | 2001-01-09 | Deoxidizing agent of molybdenum oxide and its preparing process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1302686A true CN1302686A (en) | 2001-07-11 |
| CN1111082C CN1111082C (en) | 2003-06-11 |
Family
ID=4654198
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 01105111 Expired - Fee Related CN1111082C (en) | 2001-01-09 | 2001-01-09 | Deoxidizing agent of molybdenum oxide and its preparing process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1111082C (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1332753C (en) * | 2005-06-20 | 2007-08-22 | 天津化工研究设计院 | Sulphur resisting catalyzing deoxidation agent and its production process |
| CN100402140C (en) * | 2006-07-11 | 2008-07-16 | 湖北省化学研究院 | Sulfur-proof deoxidizing agent and its preparing and use |
| CN101797508B (en) * | 2009-12-08 | 2013-02-13 | 武汉科林精细化工有限公司 | Coking oven gas hydrodesulfurization catalyst and method for preparing same |
| CN103143315A (en) * | 2013-03-13 | 2013-06-12 | 福州大学 | Deoxidizer carrier as well as sulfur-resisting deoxidizer based on carrier and preparation method of carrier |
| CN104888798A (en) * | 2015-06-10 | 2015-09-09 | 西南化工研究设计院有限公司 | High-activity catalyst for sulfur-tolerant deoxidization of CO-rich gas and preparation method of high-activity catalyst |
| CN102832047B (en) * | 2011-06-15 | 2016-04-20 | 微宏动力系统（湖州）有限公司 | Electrode material of lithium ion super capacitor and preparation method thereof |
| CN108212180A (en) * | 2018-03-20 | 2018-06-29 | 攀枝花市正源科技有限责任公司 | A kind of middle low temperature SCR denitration titanium molybdenum composite powder and preparation method thereof |
-
2001
- 2001-01-09 CN CN 01105111 patent/CN1111082C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1332753C (en) * | 2005-06-20 | 2007-08-22 | 天津化工研究设计院 | Sulphur resisting catalyzing deoxidation agent and its production process |
| CN100402140C (en) * | 2006-07-11 | 2008-07-16 | 湖北省化学研究院 | Sulfur-proof deoxidizing agent and its preparing and use |
| CN101797508B (en) * | 2009-12-08 | 2013-02-13 | 武汉科林精细化工有限公司 | Coking oven gas hydrodesulfurization catalyst and method for preparing same |
| CN102832047B (en) * | 2011-06-15 | 2016-04-20 | 微宏动力系统（湖州）有限公司 | Electrode material of lithium ion super capacitor and preparation method thereof |
| CN103143315A (en) * | 2013-03-13 | 2013-06-12 | 福州大学 | Deoxidizer carrier as well as sulfur-resisting deoxidizer based on carrier and preparation method of carrier |
| CN103143315B (en) * | 2013-03-13 | 2015-01-21 | 福州大学 | Deoxidizer carrier as well as sulfur-resisting deoxidizer based on carrier and preparation method of carrier |
| CN104888798A (en) * | 2015-06-10 | 2015-09-09 | 西南化工研究设计院有限公司 | High-activity catalyst for sulfur-tolerant deoxidization of CO-rich gas and preparation method of high-activity catalyst |
| CN108212180A (en) * | 2018-03-20 | 2018-06-29 | 攀枝花市正源科技有限责任公司 | A kind of middle low temperature SCR denitration titanium molybdenum composite powder and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1111082C (en) | 2003-06-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4210628A (en) | Removal of nitrogen oxides | |
| CN105013322B (en) | A kind of manganese oxide catalyst is used for the purposes of catalysis oxidation formaldehyde | |
| CN107442154A (en) | A kind of cryptomelane based composite metal element catalyst and its production and use | |
| CN101695651B (en) | Copper and iron-loaded modified activated carbon absorbent and method for preparing same | |
| CN108246290A (en) | A kind of catalyst of room temperature efficient removal air or formaldehyde in waste water and preparation method thereof | |
| CN104888602A (en) | Application of Metal Oxide Modified CePO4 Catalysts for Synergistic Denitrification and Mercury Removal | |
| CN113751023B (en) | Bimetallic-based catalyst for low-temperature high-selectivity catalytic oxidation of ammonia, preparation method and application thereof | |
| WO1997011779A1 (en) | Poisonous gas removing agent | |
| CN106391007A (en) | Catalyst for catalytic removal of carbon monoxide and formaldehyde under conditions of ambient temperature and humidity and preparation method of catalyst | |
| CN111097442B (en) | Flue gas synergistic denitration and demercuration catalyst and preparation method thereof | |
| CN113145111A (en) | A kind of diatomite composite catalyst and its preparation method and application | |
| CN101905162A (en) | Molecular sieve-supported cobalt-based composite oxide catalyst, preparation method and application | |
| CN101204660A (en) | A kind of deoxidation catalyst and its preparation method and application | |
| CN114950424A (en) | Circulating gas two-stage type desulfurization catalyst, preparation method and application thereof | |
| CN1111082C (en) | Deoxidizing agent of molybdenum oxide and its preparing process | |
| CN110302830A (en) | VOCs purification molecular sieve based catalyst under high humidity environment and the preparation method and application thereof | |
| CN115245820B (en) | A spinel catalyst, preparation method and application thereof | |
| CN112156779A (en) | Manganese oxide-loaded noble metal monoatomic VOC oxidation catalyst and preparation method and application thereof | |
| CN101693193A (en) | Rare earth-Cu-Fe active carbon adsorbent, preparation method and application thereof | |
| CN100402140C (en) | Sulfur-proof deoxidizing agent and its preparing and use | |
| CN1070128A (en) | A kind of palladium/manganese oxide deoxidizing agent | |
| CN111468172A (en) | A metal oxide-silver bifunctional catalyst for purifying and treating formaldehyde waste gas and preparation method thereof | |
| CN107252694B (en) | Catalyst for oxidizing CO under a water vapor and carbon dioxide atmosphere and preparation method thereof | |
| CN115138371B (en) | Selective catalytic oxidation catalyst for reducing sulfur pollutants, and preparation method and application thereof | |
| CN113877605B (en) | A catalyst for low-temperature oxidation of CO and its preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |