CN107126832A - Manganese systems composite gas deoxidier - Google Patents
Manganese systems composite gas deoxidier Download PDFInfo
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- CN107126832A CN107126832A CN201710470469.5A CN201710470469A CN107126832A CN 107126832 A CN107126832 A CN 107126832A CN 201710470469 A CN201710470469 A CN 201710470469A CN 107126832 A CN107126832 A CN 107126832A
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- 239000011572 manganese Substances 0.000 title claims abstract description 24
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 23
- 239000002131 composite material Substances 0.000 title claims abstract description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 35
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000025 natural resin Substances 0.000 claims abstract description 13
- 235000019353 potassium silicate Nutrition 0.000 claims abstract description 13
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 12
- 241001494479 Pecora Species 0.000 claims abstract description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 12
- 235000009508 confectionery Nutrition 0.000 claims abstract description 12
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 12
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002689 soil Substances 0.000 claims abstract description 12
- 235000013809 polyvinylpolypyrrolidone Nutrition 0.000 claims abstract description 11
- 229920000523 polyvinylpolypyrrolidone Polymers 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 11
- RSEIMSPAXMNYFJ-UHFFFAOYSA-N europium(III) oxide Inorganic materials O=[Eu]O[Eu]=O RSEIMSPAXMNYFJ-UHFFFAOYSA-N 0.000 claims abstract description 7
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium oxide Inorganic materials [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000001642 boronic acid derivatives Chemical class 0.000 claims abstract description 6
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 6
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 6
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 6
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 6
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 6
- 239000010453 quartz Substances 0.000 claims abstract description 4
- 239000007787 solid Substances 0.000 claims description 45
- 239000007789 gas Substances 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- 239000011521 glass Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical group O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 10
- 239000006004 Quartz sand Substances 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 229960000892 attapulgite Drugs 0.000 claims description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 229910052625 palygorskite Inorganic materials 0.000 claims description 6
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 5
- 238000007605 air drying Methods 0.000 claims description 5
- 238000007654 immersion Methods 0.000 claims description 5
- 238000011084 recovery Methods 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims 2
- 239000002253 acid Substances 0.000 claims 1
- 238000004132 cross linking Methods 0.000 claims 1
- 150000002576 ketones Chemical class 0.000 claims 1
- 229910052759 nickel Inorganic materials 0.000 claims 1
- 238000012856 packing Methods 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 230000008901 benefit Effects 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000006253 efflorescence Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 206010037844 rash Diseases 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/81—Solid phase processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention discloses carrier and 30% active component of a kind of manganese systems composite gas deoxidier, including count by weight percentage 70%, wherein, carrier includes the following raw material of part by weight：The sweet soil of 43~55 parts of aluminum oxide, 22~25 parts of kaolin, 18~21 parts of attapulgites, 15~19 parts of diatomite, 6~10 portions of sheep, 16~20 parts of natural resins, 26~31 parts of PVPPs, 11~17 parts of line borates, 5~8 parts of quartz sands, 7~11 parts of waterglass, active component include the following raw material constituted in molar ratio：MnO2：SiO2：TiO2：Eu2O3：Nd2O3=1：0.65~0.75：0.2~0.4：0.12~0.2：0.25~0.3.The characteristics of present invention has that high mechanical strength, deoxidation depth are deep, is not pulverized easily, deoxidation capacity is high, service life is long.
Description
Technical field
The present invention relates to chemical industry deoxy technology field.It is more particularly related to a kind of manganese systems composite gas deoxidation
Agent.
Background technology
The method of deoxidation that current chemical industry is used mainly has two types：The first is catalytic hydrodeoxygenation, using one
A little noble metals make catalyst, and being passed through hydrogen makes its generation water that reacts with the micro amount of oxygen in object gas, and this method is most
Big advantage is that activity is high under normal temperature, but defect is equally obvious, one be catalyst price it is high, two be in object gas
Foreign gas requires tighter, it is ensured that can not the gas containing compositions such as sulphur, chlorine to prevent catalyst poisoning, therefore, the method
Audient face is small, second be comparison more than chemical absorption method, using the metal of some strong oxidizing properties do active component with
Micro amount of oxygen reaction in object gas, reaches the purpose of deoxidation, then repeat to make by the reduction of these active components with reducibility gas
It is with the advantage of, this method with low cost, but the deoxidier in this method equally exists some problems, and one is machinery
Intensity difference, easy efflorescence, two be deoxidation depth not enough, three may be mixed into ammonia nitrogen or other easily poison active component for some
Gas, it is impossible to play good deoxidation effect, also has its exclusive defect to be reduction process simultaneously for manganese deoxidier
Easy temperature runaway reduce further the mechanical strength of deoxidier.
The content of the invention
It is an object of the present invention to provide a kind of high mechanical strength, deoxidation depth is deep, be not pulverized easily, deoxidation capacity is high,
The manganese systems composite gas deoxidier of service life length.
In order to realize according to object of the present invention and further advantage there is provided a kind of manganese systems composite gas deoxidier,
Including count by weight percentage 70% carrier and 30% active component, wherein, carrier is as follows including part by weight
Raw material：43~55 portions of aluminum oxide, 22~25 portions of kaolin, 18~21 portions of attapulgites, 15~19 portions of diatomite, 6~10 portions of sheep
Sweet soil, 16~20 parts of natural resins, 26~31 parts of PVPPs, 11~17 parts of line borates, 5~8 parts of quartz sand, 7~11 parts
Waterglass, active component includes the following raw material constituted in molar ratio：MnO2：SiO2：TiO2：Eu2O3：Nd2O3=1：0.65~
0.75：0.2~0.4：0.12~0.2：0.25~0.3.
Preferably, the one or more in nickel oxide, cobalt/cobalt oxide, chromated oxide are also added with active component.
Preferably, chromated oxide is CrO3, itself and MnO2Mol ratio be 0.33~0.4：1.
The present invention also provides the preparation method of above-mentioned manganese systems composite gas deoxidier, comprises the following steps：
Step 1: by the aluminum oxide of above-mentioned parts by weight, kaolin, attapulgite, diatomite, the sweet soil of sheep, line borate, quartz
Sand, PVPP are crushed, and are then well mixed with the sieve of 300~400 mesh；
Step 2: the natural resin of above-mentioned parts by weight and waterglass are added in mixture made from step one, it is warming up to
45~50 DEG C are stirred for uniformly, are then pressed into circular cylindrical solid by cylindrical mold, and dried at a temperature of 80~90 DEG C；
Step 3: active component is dissolved in the dilute hydrochloric acid solution that concentration is 5%, and pH value is adjusted to 3~4, then will
Circular cylindrical solid made from step 2 is dipped into the dilute hydrochloric acid solution 18~22 hours containing active component；
Step 4: by the circular cylindrical solid natural air drying after being soaked in step 3, then will be cylindrical solid with glass shell
Body sealed envelope is got up, be placed at 350~450 DEG C be calcined 2~3 hours, in roasting process uniform rotation circular cylindrical solid with
Make to be heated evenly, break glass shell after the completion of roasting into pieces；
Reduced Step 5: the circular cylindrical solid in step 4 by roasting is placed in the atmosphere of hydrogen or carbon monoxide,
Gas flow rate is 250ml/s, while stepping up gas temperature from room temperature to 100~120 DEG C, the recovery time is 5.5~6 small
When.
Preferably, the pressure suppressed in step 2 using cylindrical die is in 1.2~1.5MPa.
Preferably, the immersion process of circular cylindrical solid can also be completed using siphon distraction procedure in step 3, specific side
Method is：Dilute hydrochloric acid solution containing active component is dispensed into two tanks, the height of a tank is higher than another tank
Height, be inverted to form connection by a U-tube between two tanks, in the VERTICAL TUBE that circular cylindrical solid is placed in the U-tube, then
In U-tube siphonage will be formed full of the dilute hydrochloric acid solution containing active component.
Preferably, the VERTICAL TUBE caliber of the U-tube is identical with the diameter of section of circular cylindrical solid.
The present invention at least includes following beneficial effect：
1st, natural resin is added, that the composition such as waterglass can fix aluminum oxide, kaolin, attapulgite, diatomite, sheep is sweet
The profile of the clays such as soil, it is ensured that will not be damaged in deoxidier manufacturing process, improves mechanical strength, while also ensuring carrier
Porosity will not because of compacting or roasting processing produce large change.
2nd, the cooperation that PVPP and active component can be good, plays the deoxidation effect of long duration, while also avoiding
Mn oxide, again quickly by the dioxygen oxidation in air, is reducing the shortcoming of deoxidation capacity after being reduced.
3rd, do not poisoned by adding rare earth element with protection activity composition by ammonia nitrogen or other gases, so as to reduce deoxidation
Effect, to extend the service life of deoxidier.
4th, when carrying out deoxidier reduction pretreatment, the heating suddenly of generation can transfer heat to some low-melting-point materials
Matter, to protect the stephanoporate framework not efflorescence by high temperature action of clay formation, while the high porosity that deoxidier is kept also can be fast
High temperature is transmitted in air by speed.
Further advantage, target and the feature of the present invention embodies part by following explanation, and part will also be by this
The research and practice of invention and be understood by the person skilled in the art.
Embodiment
With reference to embodiment, the present invention is described in further detail, to make those skilled in the art with reference to specification
Word can be implemented according to this.
It should be noted that experimental method described in following embodiments, is conventional method unless otherwise specified, institute
Reagent and material are stated, unless otherwise specified, is commercially obtained.
<Embodiment 1>：
A kind of manganese systems composite gas deoxidier, includes count by weight percentage 70% carrier and 30% activearm
Point, wherein, carrier includes the following raw material of part by weight：43 parts of aluminum oxide, 22 parts of kaolin, 18 parts of attapulgites, 15 parts
The sweet soil of diatomite, 6 portions of sheep, 16 parts of natural resins, 26 parts of PVPPs, 11 parts of line borates, 5 parts of quartz sands, 7 parts of waterglass,
Active component includes the following raw material constituted in molar ratio：MnO2：SiO2：TiO2：Eu2O3：Nd2O3：CrO3=1：0.65：0.2：
0.12：0.25：0.33.
The preparation method of above-mentioned manganese systems composite gas deoxidier, comprises the following steps：
Step 1: by the aluminum oxide of above-mentioned parts by weight, kaolin, attapulgite, diatomite, the sweet soil of sheep, line borate, quartz
Sand, PVPP are crushed, and are then well mixed with the sieve of 300 mesh；
Step 2: the natural resin of above-mentioned parts by weight and waterglass are added in mixture made from step one, it is warming up to
45 DEG C are stirred for uniform, are then pressed into circular cylindrical solid by cylindrical mold, and the pressure of compacting is in 1.2MPa, and in 80 DEG C
At a temperature of dry；
Step 3: active component is dissolved in the dilute hydrochloric acid solution that concentration is 5%, and pH value is adjusted to 3, then by step
Circular cylindrical solid made from two is dipped into the dilute hydrochloric acid solution 18 hours containing active component, and immersion process was drawn using siphon
Journey is completed, and specific method is：Dilute hydrochloric acid solution containing active component is dispensed into two tanks, the height of a tank is high
It is inverted to form connection by a U-tube between the height of another tank, two tanks, circular cylindrical solid is placed in the U-tube
VERTICAL TUBE in, then will in U-tube full of the dilute hydrochloric acid solution containing active component to form siphonage, make containing activearm
The dilute hydrochloric acid solution divided is slowly infiltrated through in the hole of circular cylindrical solid, wherein, vertical bore and the cylinder of the U-tube
The diameter of section of solid is identical；
Step 4: by the circular cylindrical solid natural air drying after being soaked in step 3, then will be cylindrical solid with glass shell
Body sealed envelope is got up, and is placed in being calcined 2 hours at 350 DEG C, and uniform rotation circular cylindrical solid in roasting process is so that heated equal
It is even, break glass shell after the completion of roasting into pieces；
Reduced Step 5: the circular cylindrical solid in step 4 by roasting is placed in the atmosphere of hydrogen or carbon monoxide,
Gas flow rate is 250ml/s, while stepping up gas temperature from room temperature to 100 DEG C, the recovery time is 5.5 hours.
<Embodiment 2>：
A kind of manganese systems composite gas deoxidier, includes count by weight percentage 70% carrier and 30% activearm
Point, wherein, carrier includes the following raw material of part by weight：55 parts of aluminum oxide, 25 parts of kaolin, 21 parts of attapulgites, 19 parts
The sweet soil of diatomite, 10 portions of sheep, 20 parts of natural resins, 31 parts of PVPPs, 17 parts of line borates, 8 parts of quartz sands, 11 parts of water glass
Glass, active component includes the following raw material constituted in molar ratio：MnO2：SiO2：TiO2：Eu2O3：Nd2O3：CrO3=1：0.75：
0.4：0.2：0.3：0.4.
The preparation method of above-mentioned manganese systems composite gas deoxidier, comprises the following steps：
Step 1: by the aluminum oxide of above-mentioned parts by weight, kaolin, attapulgite, diatomite, the sweet soil of sheep, line borate, quartz
Sand, PVPP are crushed, and are then well mixed with the sieve of 400 mesh；
Step 2: the natural resin of above-mentioned parts by weight and waterglass are added in mixture made from step one, it is warming up to
50 DEG C are stirred for uniform, are then pressed into circular cylindrical solid by cylindrical mold, and the pressure of compacting is in 1.5MPa, and in 90 DEG C
At a temperature of dry；
Step 3: active component is dissolved in the dilute hydrochloric acid solution that concentration is 5%, and pH value is adjusted to 4, then by step
Circular cylindrical solid made from two is dipped into the dilute hydrochloric acid solution 22 hours containing active component, and immersion process was drawn using siphon
Journey is completed, and specific method is：Dilute hydrochloric acid solution containing active component is dispensed into two tanks, the height of a tank is high
It is inverted to form connection by a U-tube between the height of another tank, two tanks, circular cylindrical solid is placed in the U-tube
VERTICAL TUBE in, then will in U-tube full of the dilute hydrochloric acid solution containing active component to form siphonage, make containing activearm
The dilute hydrochloric acid solution divided is slowly infiltrated through in the hole of circular cylindrical solid, wherein, vertical bore and the cylinder of the U-tube
The diameter of section of solid is identical；
Step 4: by the circular cylindrical solid natural air drying after being soaked in step 3, then will be cylindrical solid with glass shell
Body sealed envelope is got up, and is placed in being calcined 3 hours at 450 DEG C, and uniform rotation circular cylindrical solid in roasting process is so that heated equal
It is even, break glass shell after the completion of roasting into pieces；
Reduced Step 5: the circular cylindrical solid in step 4 by roasting is placed in the atmosphere of hydrogen or carbon monoxide,
Gas flow rate is 250ml/s, while stepping up gas temperature from room temperature to 120 DEG C, the recovery time is 6 hours.
<Embodiment 3>：
A kind of manganese systems composite gas deoxidier, includes count by weight percentage 70% carrier and 30% activearm
Point, wherein, carrier includes the following raw material of part by weight：49 parts of aluminum oxide, 23.5 parts of kaolin, 19.5 parts of attapulgites,
The sweet soil of 17 parts of diatomite, 8 portions of sheep, 18 parts of natural resins, 28.5 parts of PVPPs, 14 parts of line borates, 6.5 parts of quartz sand, 9 parts
Waterglass, active component includes the following raw material constituted in molar ratio：MnO2：SiO2：TiO2：Eu2O3：Nd2O3：CrO3=1：
0.7：0.3：0.16：0.27：0.36.
The preparation method of above-mentioned manganese systems composite gas deoxidier, comprises the following steps：
Step 1: by the aluminum oxide of above-mentioned parts by weight, kaolin, attapulgite, diatomite, the sweet soil of sheep, line borate, quartz
Sand, PVPP are crushed, and are then well mixed with the sieve of 350 mesh；
Step 2: the natural resin of above-mentioned parts by weight and waterglass are added in mixture made from step one, it is warming up to
48 DEG C are stirred for uniform, are then pressed into circular cylindrical solid by cylindrical mold, and the pressure of compacting is in 1.35MPa, and in 85
Dried at a temperature of DEG C；
Step 3: active component is dissolved in the dilute hydrochloric acid solution that concentration is 5%, and pH value is adjusted to 3.5, then will step
Circular cylindrical solid made from rapid two is dipped into the dilute hydrochloric acid solution 20 hours containing active component, and immersion process is drawn using siphon
Process is completed, and specific method is：Dilute hydrochloric acid solution containing active component is dispensed into two tanks, the height of a tank
Higher than the height of another tank, it is inverted to form connection by a U-tube between two tanks, circular cylindrical solid is placed in the U-shaped
In the VERTICAL TUBE of pipe, then siphonage will be formed full of the dilute hydrochloric acid solution containing active component in U-tube, made containing active
The dilute hydrochloric acid solution of component is slowly infiltrated through in the hole of circular cylindrical solid, wherein, the vertical bore and cylinder of the U-tube
The diameter of section of shape solid is identical；
Step 4: by the circular cylindrical solid natural air drying after being soaked in step 3, then will be cylindrical solid with glass shell
Body sealed envelope is got up, and is placed in being calcined 2.5 hours at 410 DEG C, uniform rotation circular cylindrical solid in roasting process is so that heated
Uniformly, glass shell is broken into pieces after the completion of roasting；
Reduced Step 5: the circular cylindrical solid in step 4 by roasting is placed in the atmosphere of hydrogen or carbon monoxide,
Gas flow rate is 250ml/s, while stepping up gas temperature from room temperature to 110 DEG C, the recovery time is 5.8 hours.
<Comparative example 1>：
A kind of manganese deoxidier, its composition is same as Example 3, simply without natural resin, waterglass, preparation method
It is identical with embodiment 3.
<Comparative example 2>：
A kind of manganese deoxidier, its composition is same as Example 3, simply without Eu2O3、Nd2O3, preparation method also with reality
Apply the identical of example 3.
The deoxidation effect of testing example 1~3 and comparative example 1~2, tests gas and accounts for 70% by percent by volume respectively
H2, 20% N2, 5.8% CO, 4% SO2And 0.2% O2Composition, test condition is 5atm, room temperature, 5000hr-1, together
When the mechanical strength of embodiment 1~3 and comparative example is measured, the results are shown in Table 1.
Table 1, the deoxidizing capacity of deoxidier and mechanical strength contrast table
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | |
| Mechanical strength | 13kg/cm2 | 12kg/cm2 | 15kg/cm2 | 4.7kg/cm2 | 12kg/cm2 |
| Deoxidation depth | 0.1ppm | 0.08ppm | 0.05ppm | 0.1ppm | 5ppm |
| Deoxidation capacity | 66ml/g | 63ml/g | 71ml/g | 64ml/g | 28ml/g |
As it can be seen from table 1 the mechanical strength of deoxidier is substantially better than effect in comparative example 1 in embodiment 1~3,
Deoxidation depth and deoxidation capacity are substantially better than effect in comparative example 2.
Although embodiment of the present invention is disclosed as above, it is not restricted in specification and embodiment listed
With it can be applied to various suitable the field of the invention completely, can be easily for those skilled in the art
Other modification is realized, therefore under the universal limited without departing substantially from claim and equivalency range, the present invention is not limited
In specific details and shown here as the embodiment with description.
Claims (7)
1. a kind of manganese systems composite gas deoxidier, it is characterised in that including count by weight percentage 70% carrier and 30%
Active component, wherein, carrier includes the following raw material of part by weight：43~55 parts of aluminum oxide, 22~25 parts of kaolin, 18
The sweet soil of~21 parts of attapulgites, 15~19 parts of diatomite, 6~10 portions of sheep, 16~20 parts of natural resins, the poly- dimension of 26~31 parts of crosslinkings
Ketone, 11~17 parts of line borates, 5~8 parts of quartz sands, 7~11 parts of waterglass, active component include the following original constituted in molar ratio
Material：MnO2：SiO2：TiO2：Eu2O3：Nd2O3=1：0.65~0.75：0.2~0.4：0.12~0.2：0.25~0.3.
2. manganese systems composite gas deoxidier as claimed in claim 1, it is characterised in that also aoxidized in active component added with nickel
One or more in thing, cobalt/cobalt oxide, chromated oxide.
3. manganese systems composite gas deoxidier as claimed in claim 2, it is characterised in that chromated oxide is CrO3, itself and MnO2's
Mol ratio is 0.33~0.4：1.
4. a kind of preparation method of manganese systems composite gas deoxidier as claimed in claim 1, it is characterised in that including following step
Suddenly：
Step 1: by the aluminum oxide of above-mentioned parts by weight, kaolin, attapulgite, diatomite, the sweet soil of sheep, line borate, quartz sand,
PVPP is crushed, and is then well mixed with the sieve of 300~400 mesh；
Step 2: the natural resin of above-mentioned parts by weight and waterglass are added in mixture made from step one, it is warming up to 45~
50 DEG C are stirred for uniformly, are then pressed into circular cylindrical solid by cylindrical mold, and dried at a temperature of 80~90 DEG C；
Step 3: active component is dissolved in the dilute hydrochloric acid solution that concentration is 5%, and pH value is adjusted to 3~4, then by step
Circular cylindrical solid made from two is dipped into the dilute hydrochloric acid solution 18~22 hours containing active component；
Step 4: by step 3 soak after circular cylindrical solid natural air drying, it is then with glass shell that circular cylindrical solid is close
Package wraps, be placed at 350~450 DEG C be calcined 2~3 hours, uniform rotation circular cylindrical solid in roasting process so that by
It is hot uniform, break glass shell after the completion of roasting into pieces；
Reduced Step 5: the circular cylindrical solid in step 4 by roasting is placed in the atmosphere of hydrogen or carbon monoxide, gas
Flow velocity is 250ml/s, while stepping up gas temperature from room temperature to 100~120 DEG C, the recovery time is 5.5~6 hours.
5. the preparation method of manganese systems composite gas deoxidier as claimed in claim 4, it is characterised in that circle is used in step 2
The pressure that cylindrical mold is suppressed is in 1.2~1.5MPa.
6. the preparation method of manganese systems composite gas deoxidier as claimed in claim 4, it is characterised in that cylindrical in step 3
The immersion process of solid can also be completed using siphon distraction procedure, and specific method is：By the dilute hydrochloric acid solution containing active component
Packing is into two tanks, and the height of a tank is higher than between the height of another tank, two tanks is inverted shape by a U-tube
Into connection, in the VERTICAL TUBE that circular cylindrical solid is placed in the U-tube, then dilute salt containing active component will be full of in U-tube
Acid solution is to form siphonage.
7. the preparation method of manganese systems composite gas deoxidier as claimed in claim 6, it is characterised in that the U-tube it is perpendicular
Straight tube caliber is identical with the diameter of section of circular cylindrical solid.
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| JP2015196183A (en) * | 2014-04-02 | 2015-11-09 | 日鐵住金溶接工業株式会社 | Low hydrogen type coated electrode |
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Application publication date: 20170905 |