CN107029684B - Slow-release type long-acting gas deoxidizer and preparation method thereof - Google Patents
Slow-release type long-acting gas deoxidizer and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 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
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 claims abstract description 12
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 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
- 229960000892 attapulgite Drugs 0.000 claims abstract description 12
- 229960000913 crospovidone Drugs 0.000 claims abstract description 12
- 239000001863 hydroxypropyl cellulose Substances 0.000 claims abstract description 12
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 claims abstract description 12
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052625 palygorskite Inorganic materials 0.000 claims abstract description 12
- 235000013809 polyvinylpolypyrrolidone Nutrition 0.000 claims abstract description 12
- 229920000523 polyvinylpolypyrrolidone Polymers 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 239000000454 talc Substances 0.000 claims abstract description 12
- 229910052623 talc Inorganic materials 0.000 claims abstract description 12
- 239000006004 Quartz sand Substances 0.000 claims abstract description 11
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 11
- VLCLHFYFMCKBRP-UHFFFAOYSA-N tricalcium;diborate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]B([O-])[O-].[O-]B([O-])[O-] VLCLHFYFMCKBRP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910001928 zirconium oxide Inorganic materials 0.000 claims abstract description 11
- 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
- 239000007787 solid Substances 0.000 claims description 58
- 239000007789 gas Substances 0.000 claims description 36
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 230000000694 effects Effects 0.000 claims description 12
- 238000003825 pressing Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 239000011521 glass Substances 0.000 claims description 10
- 238000002791 soaking Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 5
- 238000005260 corrosion Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000007873 sieving Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000013268 sustained release Methods 0.000 claims 2
- 239000012730 sustained-release form Substances 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000010298 pulverizing process Methods 0.000 abstract description 3
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 235000012222 talc Nutrition 0.000 description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 239000004480 active ingredient Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000012466 permeate Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229910000423 chromium oxide Inorganic materials 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 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
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 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
- 239000013354 porous framework Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/12—Naturally occurring clays or bleaching earth
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/14—Diatomaceous earth
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/262—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation
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- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28011—Other properties, e.g. density, crush strength
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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Abstract
The invention discloses a slow-release long-acting gas deoxidizer and a preparation method thereof, wherein the deoxidizer comprises 70% of a carrier and 30% of active components by weight, wherein the carrier comprises the following raw materials in parts by weight: 43-55 parts of zirconium oxide, 22-25 parts of talc, 18-21 parts of attapulgite, 15-19 parts of diatomite, 6-10 parts of hydroxypropyl cellulose, 16-20 parts of natural resin, 26-31 parts of crospovidone, 11-17 parts of calcium borate, 5-8 parts of quartz sand and 7-11 parts of water glass, wherein the active components comprise the following raw materials in molar ratio: MnO2：ZnO：TiO2：Y2O3：Nd2O31: 0.65-0.75: 0.2-0.4: 0.12-0.2: 0.25 to 0.3. The invention has the characteristics of high mechanical strength, deep deoxidation depth, difficult pulverization, high deoxidation capacity and long service life.
Description
Technical Field
The invention relates to the technical field of chemical deoxidation. More particularly, the invention relates to a slow-release type long-acting gas deoxidizer and a preparation method thereof.
Background
The deoxidation methods currently used in the chemical industry are mainly of two types: the first is catalytic hydrodeoxygenation, which uses some noble metals as catalysts, and introduces hydrogen to react with trace oxygen in target gas to generate water, the method has the greatest advantage of high activity at normal temperature, but the defects are also obvious, the first is high cost, the second is strict requirement on impurity gas in target gas, and ensures gas which cannot contain sulfur, chlorine and other components to prevent catalyst poisoning, so the method has little audience, the second is a more-used chemical absorption method, uses some metals with strong oxidizability as active components to react with trace oxygen in target gas to achieve the aim of deoxidation, and uses reducing gas to reduce the active components for reuse, the method has the advantages of low cost, but the deoxidizer in the method has some problems, and the first is poor mechanical strength and easy pulverization, secondly, the deoxidation depth is not enough, the three needles can not play a good deoxidation effect on gases possibly mixed with ammonia nitrogen or other active ingredients easy to poison, and the manganese series deoxidizer also has a unique defect that the temperature runaway in the reduction process is easy to further reduce the mechanical strength of the deoxidizer.
Disclosure of Invention
The invention aims to provide a slow-release long-acting gas deoxidizer which has high mechanical strength, deep deoxidation depth, difficult pulverization, high deoxidation capacity and long service life.
To achieve these objects and other advantages in accordance with the present invention, there is provided a slow-release type long-acting gas deoxidizer including 70% by weight of a carrier and 30% by weight of an active ingredient, wherein the carrier includes the following raw materials in parts by weight: 43-55 parts of zirconium oxide, 22-25 parts of talc, 18-21 parts of attapulgite, 15-19 parts of diatomite, 6-10 parts of hydroxypropyl cellulose, 16-20 parts of natural resin, 26-31 parts of crospovidone, 11-17 parts of calcium borate, 5-8 parts of quartz sand and 7-11 parts of water glass, wherein the active components comprise the following raw materials in molar ratio: MnO2：ZnO：TiO2：Y2O3：Nd2O3＝1：0.65～0.75：0.2～0.4：0.12～0.2：0.25～0.3。
Preferably, one or more of nickel oxide, cobalt oxide and chromium oxide is/are further added into the active component.
Preferably, the chromium oxide is CrO3With MnO of2In a molar ratio of 0.33 to 0.4: 1.
the invention also provides a preparation method of the slow-release type long-acting gas deoxidizer, which comprises the following steps:
crushing the zirconium oxide, the talc, the attapulgite, the diatomite, the hydroxypropyl cellulose, the calcium borate, the quartz sand and the crospovidone in parts by weight, and then sieving and uniformly mixing the crushed materials by using a 300-400-mesh sieve;
step two, adding the natural resin and the water glass in parts by weight into the mixture prepared in the step one, heating to 45-50 ℃, uniformly stirring, pressing into a cylindrical solid through a cylindrical die, and drying at the temperature of 80-90 ℃;
dissolving the active component in a dilute hydrochloric acid solution with the concentration of 5%, adjusting the pH value to 3-4, and then soaking the cylindrical solid prepared in the step two in the dilute hydrochloric acid solution containing the active component for 18-22 hours;
step four, naturally drying the cylindrical solid soaked in the step three, then hermetically wrapping the cylindrical solid by using a glass shell, roasting the cylindrical solid at 350-450 ℃ for 2-3 hours, uniformly rotating the cylindrical solid in the roasting process to uniformly heat the cylindrical solid, and breaking the glass shell after roasting is finished;
and step five, placing the cylindrical solid roasted in the step four in an atmosphere of hydrogen or carbon monoxide for reduction, wherein the gas flow rate is 250ml/s, the gas temperature is gradually increased from room temperature to 100-120 ℃, and the reduction time is 5.5-6 hours.
Preferably, the pressure for pressing by using the cylindrical die in the second step is 1.2-1.5 MPa.
Preferably, the soaking process of the cylindrical solid in the third step can be completed by adopting a siphon traction process, and the specific method comprises the following steps: the method comprises the steps of subpackaging dilute hydrochloric acid solution containing active components into two water tanks, wherein the height of one water tank is higher than that of the other water tank, the two water tanks are communicated in an inverted mode through a U-shaped pipe, a cylindrical solid is placed in a vertical pipe of the U-shaped pipe, and then the U-shaped pipe is filled with the dilute hydrochloric acid solution containing the active components to form a siphoning effect.
Preferably, the diameter of the vertical pipe of the U-shaped pipe is the same as the diameter of the cross section of the cylindrical solid.
The invention at least comprises the following beneficial effects:
1. the natural resin, the water glass and other components are added to fix the shapes of the zirconia, the talc, the attapulgite, the diatomite and other clays, so that the deoxidant is not damaged in the preparation process, the mechanical strength of the zirconia after roasting is high, and the porosity of the carrier is not greatly changed due to pressing or roasting processing.
2. The crospovidone, the hydroxypropyl cellulose and the active ingredients can be well matched to play a long-term and continuous deoxidation effect, and meanwhile, the defects that the manganese oxide is quickly oxidized by oxygen in the air after being reduced and the deoxidation capacity is reduced are avoided.
3. The yttrium and neodymium elements are added to protect the manganese from being poisoned by ammonia nitrogen or other gases, so that the deoxidation effect is reduced, and the service life of the deoxidizer is prolonged.
4. When the deoxidizer is subjected to reduction pretreatment, the generated sudden temperature rise can transfer heat to some low-melting-point substances so as to protect a porous framework formed by the clay from being pulverized by high temperature, and meanwhile, the high porosity of the deoxidizer can quickly conduct high temperature to the air.
5. The micro-corrosion treatment of the hydrochloric acid aerial fog can increase the porosity of the cylindrical solid formed by the carrier, adsorb more transitional components and further improve the deoxidation effect.
6. The addition of chromium to the active ingredient further increases the deoxidizing effect of the deoxidizer and the temperature breadth of use.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Detailed Description
The present invention is further described in detail below with reference to examples so that those skilled in the art can practice the invention with reference to the description.
It is to be noted that the experimental methods described in the following embodiments are all conventional methods unless otherwise specified, and the reagents and materials are commercially available unless otherwise specified.
< example 1 >:
a slow-release long-acting gas deoxidizer comprises 70% of a carrier and 30% of an active component by weight percent, wherein the carrier comprises the following raw materials in parts by weight: 43 parts of zirconium oxide, 22 parts of talc, 18 parts of attapulgite, 15 parts of diatomite, 6 parts of hydroxypropyl cellulose, 16 parts of natural resin, 26 parts of crospovidone, 11 parts of calcium borate, 5 parts of quartz sand and 7 parts of water glass, wherein the active components comprise the following raw materials in molar ratio: MnO2：ZnO：TiO2：Y2O3：Nd2O3：CrO3＝1：0.65：0.2：0.12：0.25：0.33。
The preparation method of the slow-release long-acting gas deoxidizer comprises the following steps:
crushing the zirconium oxide, the talc, the attapulgite, the diatomite, the hydroxypropyl cellulose, the calcium borate, the quartz sand and the crospovidone in parts by weight, and then sieving and uniformly mixing the crushed materials by using a 300-mesh sieve;
step two, adding the natural resin and the water glass in parts by weight into the mixture prepared in the step one, heating to 45 ℃, uniformly stirring, pressing into a cylindrical solid through a cylindrical die, wherein the pressing pressure is 1.2MPa, drying at the temperature of 80 ℃, and then placing the cylindrical solid into hydrochloric acid aerial fog for surface micro-corrosion treatment;
step three, dissolving the active component in a dilute hydrochloric acid solution with the concentration of 5%, adjusting the pH value to 3, then soaking the cylindrical solid prepared in the step two in the dilute hydrochloric acid solution containing the active component for 18 hours, wherein the soaking process is completed by adopting a siphon traction process, and the specific method comprises the following steps: the method comprises the following steps of subpackaging dilute hydrochloric acid solution containing active components into two water tanks, wherein the height of one water tank is higher than that of the other water tank, the two water tanks are communicated in an inverted mode through a U-shaped pipe, a cylindrical solid is placed in a vertical pipe of the U-shaped pipe, then the U-shaped pipe is filled with the dilute hydrochloric acid solution containing the active components to form a siphoning effect, and the dilute hydrochloric acid solution containing the active components slowly permeates into pores of the cylindrical solid, wherein the inner diameter of the vertical pipe of the U-shaped pipe is the same as the diameter of the section of the cylindrical solid;
step four, naturally drying the cylindrical solid soaked in the step three, then sealing and wrapping the cylindrical solid by using a glass shell, roasting the cylindrical solid at 350 ℃ for 2 hours, uniformly rotating the cylindrical solid in the roasting process to ensure uniform heating, and breaking the glass shell after roasting is finished;
and step five, placing the cylindrical solid roasted in the step four in an atmosphere of hydrogen or carbon monoxide for reduction, wherein the gas flow rate is 250ml/s, the gas temperature is gradually increased from room temperature to 100 ℃, and the reduction time is 5.5 hours.
< example 2 >:
a kind of slowThe release type long-acting gas deoxidizer comprises 70 percent of carrier and 30 percent of active component by weight percent, wherein the carrier comprises the following raw materials in parts by weight: 55 parts of zirconium oxide, 25 parts of talcum, 21 parts of attapulgite, 19 parts of diatomite, 10 parts of hydroxypropyl cellulose, 20 parts of natural resin, 31 parts of crospovidone, 17 parts of calcium borate, 8 parts of quartz sand and 11 parts of water glass, wherein the active components comprise the following raw materials in molar ratio: MnO2：ZnO：TiO2：Y2O3：Nd2O3：CrO3＝1：0.75：0.4：0.2：0.3：0.4。
The preparation method of the slow-release long-acting gas deoxidizer comprises the following steps:
crushing the zirconium oxide, the talc, the attapulgite, the diatomite, the hydroxypropyl cellulose, the calcium borate, the quartz sand and the crospovidone in parts by weight, and then sieving and uniformly mixing the crushed materials by using a 400-mesh sieve;
step two, adding the natural resin and the water glass in parts by weight into the mixture prepared in the step one, heating to 50 ℃, uniformly stirring, pressing into a cylindrical solid through a cylindrical die, wherein the pressing pressure is 1.5MPa, drying at the temperature of 90 ℃, and then placing the cylindrical solid into hydrochloric acid aerial fog for surface micro-corrosion treatment;
step three, dissolving the active component in a dilute hydrochloric acid solution with the concentration of 5%, adjusting the pH value to 4, then soaking the cylindrical solid prepared in the step two in the dilute hydrochloric acid solution containing the active component for 22 hours, wherein the soaking process is completed by adopting a siphon traction process, and the specific method comprises the following steps: the method comprises the following steps of subpackaging dilute hydrochloric acid solution containing active components into two water tanks, wherein the height of one water tank is higher than that of the other water tank, the two water tanks are communicated in an inverted mode through a U-shaped pipe, a cylindrical solid is placed in a vertical pipe of the U-shaped pipe, then the U-shaped pipe is filled with the dilute hydrochloric acid solution containing the active components to form a siphoning effect, and the dilute hydrochloric acid solution containing the active components slowly permeates into pores of the cylindrical solid, wherein the inner diameter of the vertical pipe of the U-shaped pipe is the same as the diameter of the section of the cylindrical solid;
step four, naturally drying the cylindrical solid soaked in the step three, then sealing and wrapping the cylindrical solid by using a glass shell, roasting the cylindrical solid at 450 ℃ for 3 hours, uniformly rotating the cylindrical solid in the roasting process to ensure uniform heating, and breaking the glass shell after roasting is finished;
and step five, placing the cylindrical solid roasted in the step four in an atmosphere of hydrogen or carbon monoxide for reduction, wherein the gas flow rate is 250ml/s, the gas temperature is gradually increased from room temperature to 120 ℃, and the reduction time is 6 hours.
< example 3 >:
a slow-release long-acting gas deoxidizer comprises 70% of a carrier and 30% of an active component by weight percent, wherein the carrier comprises the following raw materials in parts by weight: 49 parts of zirconium oxide, 23.5 parts of talc, 19.5 parts of attapulgite, 17 parts of diatomite, 8 parts of hydroxypropyl cellulose, 18 parts of natural resin, 28.5 parts of crospovidone, 14 parts of calcium borate, 6.5 parts of quartz sand and 9 parts of water glass, wherein the active components comprise the following raw materials in mol ratio: MnO2：ZnO：TiO2：Y2O3：Nd2O3：CrO3＝1：0.7：0.3：0.16：0.27：0.36。
The preparation method of the slow-release long-acting gas deoxidizer comprises the following steps:
crushing the zirconium oxide, the talc, the attapulgite, the diatomite, the hydroxypropyl cellulose, the calcium borate, the quartz sand and the crospovidone in parts by weight, and then sieving and uniformly mixing the crushed materials by using a 350-mesh sieve;
step two, adding the natural resin and the water glass in parts by weight into the mixture prepared in the step one, heating to 48 ℃, uniformly stirring, pressing into a cylindrical solid through a cylindrical die, wherein the pressing pressure is 1.35MPa, drying at the temperature of 85 ℃, and then placing the cylindrical solid into hydrochloric acid aerial fog for surface micro-corrosion treatment;
step three, dissolving the active component in a dilute hydrochloric acid solution with the concentration of 5%, adjusting the pH value to 3.5, then soaking the cylindrical solid prepared in the step two in the dilute hydrochloric acid solution containing the active component for 20 hours, wherein the soaking process is finished by adopting a siphon traction process, and the specific method comprises the following steps: the method comprises the following steps of subpackaging dilute hydrochloric acid solution containing active components into two water tanks, wherein the height of one water tank is higher than that of the other water tank, the two water tanks are communicated in an inverted mode through a U-shaped pipe, a cylindrical solid is placed in a vertical pipe of the U-shaped pipe, then the U-shaped pipe is filled with the dilute hydrochloric acid solution containing the active components to form a siphoning effect, and the dilute hydrochloric acid solution containing the active components slowly permeates into pores of the cylindrical solid, wherein the inner diameter of the vertical pipe of the U-shaped pipe is the same as the diameter of the section of the cylindrical solid;
step four, naturally drying the cylindrical solid soaked in the step three, then sealing and wrapping the cylindrical solid by using a glass shell, roasting the cylindrical solid at the temperature of 410 ℃ for 2.5 hours, uniformly rotating the cylindrical solid in the roasting process to uniformly heat the cylindrical solid, and breaking the glass shell after the roasting is finished;
and step five, placing the cylindrical solid roasted in the step four in an atmosphere of hydrogen or carbon monoxide for reduction, wherein the gas flow rate is 250ml/s, and simultaneously gradually increasing the gas temperature from room temperature to 110 ℃ for 5.8 hours.
< comparative example 1 >:
a manganese-based deoxidizer was produced in the same manner as in example 3 except that zirconia, a natural resin and water glass were not contained in the deoxidizer, and the deoxidizer was produced in the same manner as in example 3.
< comparative example 2 >:
a manganese-based deoxidizer having the same composition as in example 3 except that Y is not contained2O3、Nd2O3、CrO3The preparation method is also the same as that of example 3.
The deoxidation effects of examples 1-3 and comparative examples 1-2 were tested separately, with the test gas consisting of 70% by volume of H220% of N25.8% of CO and 4% of SO2And 0.2% of O2The composition is tested at 5atm, room temperature, 5000hr-1The mechanical strength of examples 1 to 3 and comparative example were measured at the same time, and the results are shown in Table 1.
TABLE 1 comparative table of deoxidizing ability and mechanical strength of deoxidizing agent
| Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | |
| Mechanical strength | 14kg/cm2 | 13kg/cm2 | 16kg/cm2 | 4.2kg/cm2 | 13kg/cm2 |
| Depth of deoxidation | 0.07ppm | 0.08ppm | 0.01ppm | 0.1ppm | 1ppm |
| Capacity of deoxidation | 55ml/g | 59ml/g | 62ml/g | 56ml/g | 30ml/g |
As can be seen from Table 1, the deoxidizers of examples 1 to 3 were significantly superior in mechanical strength to those of comparative example 1, and in the deoxidation depth and the deoxidation capacity to those of comparative example 2.
While embodiments of the invention have been described above, it is not limited to the applications set forth in the description and the embodiments, which are fully applicable to various fields of endeavor for which the invention may be embodied with additional modifications as would be readily apparent to those skilled in the art, and the invention is therefore not limited to the details given herein and to the embodiments shown and described without departing from the generic concept as defined by the claims and their equivalents.
Claims (4)
1. The preparation method of the slow-release type long-acting gas deoxidizer is characterized in that the slow-release type long-acting gas deoxidizer comprises 70% of a carrier and 30% of an active component by weight percent, wherein the carrier comprises the following raw materials in parts by weight: 43-55 parts of zirconium oxide, 22-25 parts of talc, 18-21 parts of attapulgite, 15-19 parts of diatomite, 6-10 parts of hydroxypropyl cellulose, 16-20 parts of natural resin, 26-31 parts of crospovidone, 11-17 parts of calcium borate, 5-8 parts of quartz sand and 7-11 parts of water glass, wherein the active components comprise the following raw materials in molar ratio: MnO2：ZnO：TiO2：Y2O3：Nd2O31: 0.65-0.75: 0.2-0.4: 0.12-0.2: 0.25 to 0.3, CrO is also added into the active component3With MnO of2In a molar ratio of 0.33 to 0.4: 1;
the preparation method of the slow-release type long-acting gas deoxidizer comprises the following steps:
crushing the zirconium oxide, the talc, the attapulgite, the diatomite, the hydroxypropyl cellulose, the calcium borate, the quartz sand and the crospovidone in parts by weight, and then sieving and uniformly mixing the crushed materials by using a 300-400-mesh sieve;
step two, adding the natural resin and the water glass in parts by weight into the mixture prepared in the step one, heating to 45-50 ℃, uniformly stirring, pressing into a cylindrical solid through a cylindrical die, drying at 80-90 ℃, and placing the cylindrical solid into hydrochloric acid aerial fog for surface micro-corrosion treatment;
dissolving the active component in a dilute hydrochloric acid solution with the concentration of 5%, adjusting the pH value to 3-4, and then soaking the cylindrical solid prepared in the step two in the dilute hydrochloric acid solution containing the active component for 18-22 hours;
step four, naturally drying the cylindrical solid soaked in the step three, then hermetically wrapping the cylindrical solid by using a glass shell, roasting the cylindrical solid at 350-450 ℃ for 2-3 hours, uniformly rotating the cylindrical solid in the roasting process to uniformly heat the cylindrical solid, and breaking the glass shell after roasting is finished;
and step five, placing the cylindrical solid roasted in the step four in an atmosphere of hydrogen or carbon monoxide for reduction, wherein the gas flow rate is 250ml/s, the gas temperature is gradually increased from room temperature to 100-120 ℃, and the reduction time is 5.5-6 hours.
2. The method for preparing a sustained-release long-acting gas deoxidizer according to claim 1, wherein the pressure for pressing by using a cylindrical mold in the second step is 1.2 to 1.5 MPa.
3. The preparation method of the slow-release long-acting gas deoxidizer of claim 1 is characterized in that the soaking process of the cylindrical solid in the step three is completed by adopting a siphon traction process, and the specific method comprises the following steps: the method comprises the steps of subpackaging dilute hydrochloric acid solution containing active components into two water tanks, wherein the height of one water tank is higher than that of the other water tank, the two water tanks are communicated in an inverted mode through a U-shaped pipe, a cylindrical solid is placed in a vertical pipe of the U-shaped pipe, and then the U-shaped pipe is filled with the dilute hydrochloric acid solution containing the active components to form a siphoning effect.
4. The method for producing a sustained-release long-acting gas deoxidizer of claim 3, wherein the vertical tube diameter of the U-shaped tube is the same as the cross-sectional diameter of the cylindrical solid.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006326478A (en) * | 2005-05-25 | 2006-12-07 | Toyota Motor Corp | Oxygen absorbing and releasing material for cleaning emission gas, and catalyst for cleaning emission gas |
| CN1955150A (en) * | 2005-10-28 | 2007-05-02 | 中国石油化工股份有限公司 | Manganese deoxidier and its preparation method and application |
| CN104775000A (en) * | 2015-03-25 | 2015-07-15 | 芜湖华炀炉料科技有限公司 | Calcium deoxidizer using dolomite as refractory component and preparation method thereof |
| CN105363406A (en) * | 2014-08-18 | 2016-03-02 | 王雅坤 | Multifunctional deoxidizer, preparation and applications thereof |
| CN106378144A (en) * | 2016-08-16 | 2017-02-08 | 大连凯特利催化工程技术有限公司 | A manganese deoxidizer adopting a cerium-based oxide as a carrier, a preparing method thereof and applications of the deoxidizer |
-
2017
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006326478A (en) * | 2005-05-25 | 2006-12-07 | Toyota Motor Corp | Oxygen absorbing and releasing material for cleaning emission gas, and catalyst for cleaning emission gas |
| CN1955150A (en) * | 2005-10-28 | 2007-05-02 | 中国石油化工股份有限公司 | Manganese deoxidier and its preparation method and application |
| CN105363406A (en) * | 2014-08-18 | 2016-03-02 | 王雅坤 | Multifunctional deoxidizer, preparation and applications thereof |
| CN104775000A (en) * | 2015-03-25 | 2015-07-15 | 芜湖华炀炉料科技有限公司 | Calcium deoxidizer using dolomite as refractory component and preparation method thereof |
| CN106378144A (en) * | 2016-08-16 | 2017-02-08 | 大连凯特利催化工程技术有限公司 | A manganese deoxidizer adopting a cerium-based oxide as a carrier, a preparing method thereof and applications of the deoxidizer |
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