CN1785477A - Nano-deoxidant composition and its synthesis method - Google Patents
Nano-deoxidant composition and its synthesis method Download PDFInfo
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- 239000000203 mixture Substances 0.000 title claims description 12
- 238000001308 synthesis method Methods 0.000 title description 4
- 239000011656 manganese carbonate Substances 0.000 claims abstract description 41
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims abstract description 41
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 229940093474 manganese carbonate Drugs 0.000 claims description 16
- 235000006748 manganese carbonate Nutrition 0.000 claims description 16
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- -1 polyethylene Polymers 0.000 claims description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 11
- 238000005096 rolling process Methods 0.000 claims description 11
- 239000004698 Polyethylene Substances 0.000 claims description 10
- 239000002202 Polyethylene glycol Substances 0.000 claims description 10
- 229920000573 polyethylene Polymers 0.000 claims description 10
- 229920001223 polyethylene glycol Polymers 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 9
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 9
- 239000011230 binding agent Substances 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000012752 auxiliary agent Substances 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 claims description 6
- 239000004568 cement Substances 0.000 claims description 6
- 239000011572 manganese Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 238000004448 titration Methods 0.000 claims description 6
- 238000004090 dissolution Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 4
- 239000000853 adhesive Substances 0.000 claims description 3
- 230000001070 adhesive effect Effects 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 125000005594 diketone group Chemical group 0.000 claims description 2
- 238000009826 distribution Methods 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 239000008188 pellet Substances 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 5
- 229920000098 polyolefin Polymers 0.000 abstract description 5
- 230000001172 regenerating effect Effects 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 238000002360 preparation method Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 8
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 8
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 8
- 239000001099 ammonium carbonate Substances 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 238000009775 high-speed stirring Methods 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 7
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- 238000001994 activation Methods 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- 238000011069 regeneration method Methods 0.000 description 4
- 238000001694 spray drying Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 230000003635 deoxygenating effect Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 239000012756 surface treatment agent Substances 0.000 description 2
- 239000005909 Kieselgur Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
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Abstract
A nano-class deoxidizing agent for selectively removing O2 during the synthesis of polyolefin is prepared through preparing nano-MnCO3 and proportionally adding carrier and assistant. Its advantages are high deoxidizing effect and low regenerating temp.
Description
Technical Field
The invention relates to an important technical invention in the polyolefin industry field, in particular to a nano deoxidizer composition and a synthesis method thereof, which are applied to the production of polyethylene and polypropylene in the petrochemical industry to deeply remove impurity oxygen in ethylene and propylene so as to ensure the normal operation of polymerization reaction and improve the product quality. It can also be used in metallurgy, electronics, light industry and other fields to provide oxygen-free protective gas, carrying gas and reaction gas.
Background
In the production process of polyethylene and polypropylene, the polymerization reaction catalyst requires deep deoxidation of ethylene and propylene to ensure production.
The difficulty in deoxygenating olefins is that the double bonds in the olefins should not be destroyed while deoxygenating. While introducing polyethylene technology, China also purchases American UCC-1101 deoxidizer, the main component of which is Cu/SiO2Although the deoxidation depth is better (0.1ppm) and can meet the requirements of the polymerization process, the deoxidation capacity is small, the regeneration is frequent, the sintering is easy, the production is inconvenient, and the benefit is reduced. Meanwhile, the deoxidizer with low mechanical strength is seriously damaged by frequent regeneration, and the inactivation is accelerated. Therefore, the polyethylene industry urgently needs a high-efficiency deoxidizer which has excellent performance, low price and independent intellectual property rights in China to replace UCC-1101.
In the productionof polypropylene, about 40 percent of the output of China comes from small bulk polypropylene, the process is a unique process flow developed aiming at the utilization of refinery gas propylene in China, and the requirement on purification is more urgent because the oxygen content of the raw material propylene is high. No high-efficiency and high-selectivity deoxidizer product for propylene liquid phase deoxidation at home and abroad. In actual production, a nickel-based hydrogenation catalyst has only to be selected as a substitute for a deoxidizer, and therefore, the following disadvantages exist: firstly, the deoxidation depth is not enough, and the oxygen concentration in the raw material after purification is still more than 2ppm, thus greatly increasing the consumption of expensive polymerization catalyst, increasing the cost and reducing the product quality. Secondly, because nickel has typical hydrogen adsorption and hydrogenation performances, the hydrogen adsorption strength in the activation process is high, the hydrogen is not easy to blow off, and when the raw material propylene enters the purification tower, the side reaction of hydrogenation is easy to occur, and a large amount of reaction heat is released. Improper control can cause tower-burning accidents due to temperature runaway. The domestic urgent need for a high-efficiency and high-selectivity deoxidizer suitable for liquid-phase deoxidation of crude propylene.
The development of a novel high-efficiency deoxidizer is an urgent need in the polyolefin industry of China, and the institute of chemical and physical in the great chain of the Chinese academy of sciences explores from the beginning of the last 90 th century, so that the novel high-efficiency deoxidizer is successfully developed, is produced by great Saint Meyer chemical company, and meets the requirements of domestic users. The deoxidizer has good deoxidizing effect and high deoxidizing capacity. However, when the activation regeneration temperature is required to be less than or equal to 200 ℃ in the polyethylene production process, the deoxidation capacity of the manganese deoxidizer is reduced, and the application range has certain limitation. On the basis, the invention also discloses a nano deoxidizer, which endows the product with new functions.
Disclosure of Invention
The invention aims to provide a nano deoxidizer composition and a synthesis method thereof, which are used for preparing nano MnCO3Starting from the nano MnCO3The surface treatment of the said process can raise surface activity and the nano deoxidant is synthesized through the design of the recipe.
The technical scheme of the invention is as follows:
a nano deoxidant composition contains nano MnCO as main active body3And adding ZnO and Cu2O active component, which takes diatomite, alumina or high alumina cement as a support carrier; nano MnCO in weight portion360-90 parts by MnO; ZnO and Cu27-20 parts of O respectively; 0-40 parts of diatomite, alumina or high alumina cement and 2-30 parts of other auxiliary agents.
The auxiliary agent adopts a conventional auxiliary agent and comprises 1-25 parts of surface treating agent and 1-5 parts of binder.
The surface treating agent is polyethylene diketone, polyethylene glycol or polycarbonate; the binder is a polyglycol.
The synthesis method of the nano deoxidizer comprises the following steps:
1) common manganese carbonate (manganese ore powder) is adopted as a raw material, and the nano MnCO is synthesized by acid dissolution3；MnCO3The purity is more than or equal to 99 percent, the surface ofthe powder is organically treated by a surface treating agent, and the particle size distribution D90 is less than or equal to 100 nm;
2) nano MnCO3Adding intoZnO、Cu2O and adhesive, grinding, rolling ball and roasting to obtain the product.
In the step 1), the manganese carbonate is dissolved by hydrochloric acid to generate MnCl2After, with NH4HCO3Titration reaction, the two materials have the same titration speed and the molar ratio of 1: 2, stirring is carried out during the reaction, the temperature is 40-100 ℃, and the constant temperature is keptThe time is 1-4 hours.
In the step 2), the materials are mixed in a stirring mixer, processed into balls by using a roller granulator, and then roasted at the temperature of 300-450 ℃ for 1-4 hours to obtain black pellets with the shape of phi 3-5mm, wherein the surface of the deoxidizer is smooth and flat.
The weight percentage of Mn as an active component in the deoxidizer is 22-44%.
The ZnO and Cu2O and other active components, and a commercial product.
The invention has the following beneficial effects:
(1) nano MnCO3The preparation technique of (1).
The technology adopts common manganese carbonate raw material which is abundant in China and is easily obtained as manganese resource, firstly uses hydrochloric acid to dissolve the common manganese carbonate raw material, and then uses the common manganese carbonate raw material and NH4HCO3Carrying out the same-speed titration reaction, and adding quantitative polyethylene dione to obtain nano MnCO with the purity of more than 99 percent and surface activation treatment3. The technology is not reported in the literature at present.
(2) The formula design technology of the nano deoxidizer.
Adopts nano MnCO3ZnO and Cu are selected as active components2O, etc. as a support carrier. The optimum weight percentage of the active metal Mn is determined to be 22-44%. The nano deoxidizer designed by the formula has the following technical characteristics: the method is suitable for purifying olefin serving as a raw material in the polyolefin industry, and high-selectivity deoxidation is performed without damaging double-bond compounds; the deoxidation depth is deep, and the residual oxygen can be less than or equal to 0.1 ppm; the deoxidation capacity is high, and the oxygen amount per gram of deoxidizer can be 15-30 mL; the heat-resistant temperature is high, and sintering failure does not occur at 450 ℃; the service life is more than or equal to 5 years.
Drawings
FIG. 1 is a schematic view of the process of the present invention.
Detailed Description
As shown in FIG. 1, a conventional manganese carbonate raw material is dissolved with hydrochloric acid and then mixed with NH4HCO3Carrying out the same-speed titration reaction, and adding polyethylene glycol to obtain nano MnCO3In the dried MnCO3In (1), ZnO and Cu are added2O, adhesive, diatomite, alumina, high-alumina cement, etc. and through grinding, rolling and roasting to obtain the nanometer deoxidant. The invention relates to the prepared nano MnCO3Is a main active component, and is added with proper carriers and auxiliary agents to realize the high-efficiency selective removal of impurity oxygen in the polyolefin synthesis process, and simultaneously olefin double is not damagedA key. The deoxidizer utilizes the nanometer size effect, improves the deoxidizing activity of active components, and has the characteristics of low activation regeneration temperature, high deoxidizing capacity, deep deoxidizing depth, long service cycle, wide application range and the like. The high selectivity is reacted with oxygen to generate high valence oxide and realize deep deoxidation; after the catalyst is out of work, the catalyst can be activated by hydrogen to regenerate and recover the deoxidation activity.
Example 1
The method comprises the following steps: nano MnCO3Preparation of
The reaction formula is as follows:
a: 0.5mol of manganese carbonate is added into 30ml of water, and hydrochloric acid is dripped according to the molar ratio of 1: 2;
b: adding 250ml of water into 1.0mol of ammonium bicarbonate; the molar ratio of the manganese carbonate to the ammonium bicarbonate is 1: 2;
c: 5g of polyethylene glycol (surface treatment agent) was added to 100ml of water.
Placing C into a reaction bottle (with 2 dripping ports) equipped with high-speed stirring, heating to 40 deg.C for dissolving completely, dripping A, B into C at constant speed of 1 drop/second, and stirring at high speed100-120 r/min), reacting at 40 ℃ for 1 hour, filtering the generated white precipitate, washing with deionized water until no chloride ion exists, and spray drying to obtain 30-100 nm MnCO3。
Step two: synthesis of nano deoxidant
Weighing 80 g of nano MnCO subjected to surface treatment310g of ZnO and 10g of Cu2O, 20 g of diatomaceous earth, 1 g of polyethylene glycol (binder) was added and ground in a grinding dish.
Step three: preparation of nano deoxidant
Rolling the ground mixture into balls in a ball rolling device, wherein the particle size is phi 3-5mm, roasting in a furnace type reactor, and treating at 300 ℃ for 2 hours to obtain the product.
Example 2
The method comprises the following steps: nano MnCO3Preparation of
The reaction formula is as follows:
a: 0.5mol of manganese carbonate is added into 30ml of water, and hydrochloric acid is dripped according to the molar ratio of 1: 2;
b: adding 250ml of water into 1.0mol of ammonium bicarbonate; the molar ratio of the manganese carbonate to the ammonium bicarbonate is 1: 2;
c: 3g of polyethylene glycol (surface treatment agent) was added to 100ml of water.
Placing C into a reaction bottle (with 2 dropping ports) equipped with high-speed stirring, heating to 40 deg.C for complete dissolution, respectively dropping A, B into C at constant speed of 1 drop/second, reacting at 40 deg.C for 2 hr under high-speed stirring (rotation speed of 100 plus 120 rpm), filtering the generated white precipitate, washing with deionized water until no chloride ion is generated, and spray drying to obtain 30-100 nm MnCO3。
Step two: synthesis of nano deoxidant
Weighing 90 g of nano MnCO315 g of ZnO and 10g of Cu2O, 10g of aluminous cement, 2 g of polyethylene glycol (binder) was added and ground in a grinding dish.
Step three: preparation of nano deoxidant
Rolling the ground mixture into balls in a ball rolling device, wherein the particle size is phi 3-5mm, roasting in a furnace type reactor, and treating at 350 ℃ for 3 hours to obtain the product.
Example 3
The method comprises the following steps: nano MnCO3Preparation of
The reaction formula is as follows:
a: 0.5mol of manganese carbonate is added into 30ml of water, and hydrochloric acid is dripped according to the molar ratio of 1: 2;
b: adding 250ml of water into 1.0mol of ammonium bicarbonate; the molar ratio of the manganese carbonate to the ammonium bicarbonate is 1: 2;
c: 6g of polyethylene dione (surface treating agent) was added to 100ml of water.
Placing C into a reaction bottle (with 2 dropping ports) equipped with high-speed stirring, heating to 40 deg.C for complete dissolution, respectively dropping A, B into C at constant speed of 1 drop/second, reacting at 40 deg.C for 3 hr under high-speed stirring (rotation speed of 100 plus 120 rpm), filtering the generated white precipitate, washing with deionized water until no chloride ion is generated, and spray drying to obtain 30-100 nm MnCO3。
Step two: synthesis of nano deoxidant
Weighing 100 g of nano MnCO315 g of ZnO and 15 g of Cu2O, 5gof alumina, 2 g of polyethylene glycol (binder) were added and ground in a grinding dish.
Step three: preparation of nano deoxidant
Rolling the ground mixture into balls in a ball rolling device, wherein the particle size is phi 3-5mm, roasting in a furnace type reactor, and treating at 400 ℃ for 4 hours to obtain the product.
Example 4
The method comprises the following steps: nano MnCO3Preparation of
The reaction formula is as follows:
a: 0.75mol of manganese carbonate is added into 30ml of water, and hydrochloric acid is dripped according to the molar ratio of 1: 2;
b: adding 1.5mol of ammonium bicarbonate into 250ml of water; the molar ratio of the manganese carbonate to the ammonium bicarbonate is 1: 2;
c: 10g of polyethylene dione were added to 100ml of water.
Placing C into a reaction bottle (with 2 dropping ports) equipped with high-speed stirring, heating to 40 deg.C for complete dissolution, respectively dropping A, B into C at constant speed of 1 drop/second, reacting at 40 deg.C for 4 hr under high-speed stirring (rotation speed of 100 plus 120 rpm), filtering the generated white precipitate, washing with deionized water until no chloride ion is generated, and spray drying to obtain 30-100 nm MnCO3。
Step two: synthesis of nano deoxidant
Weighing 80 g of nano MnCO38 g of ZnO and 8 g of Cu2O, 1 g of polyethylene glycol (binder) was added and ground in a grinding dish.
Step three: preparation of nano deoxidant
Rolling the ground mixture into balls in a ball rolling device, wherein the particle size is phi 3-5mm, roasting in a furnace type reactor, and treating at 450 ℃ for 2 hours to obtain the product.
Claims (7)
1. A nano deoxidizer composition, which is characterized in that: the main active body is nano MnCO3And adding ZnO and Cu2O active component, which takes diatomite, alumina or high alumina cement as a support carrier; nano MnCO in weight portion360-90 parts by MnO; ZnO and Cu27-20 parts of O respectively; 0-40 parts of diatomite, alumina or high alumina cement and 2-30 parts of other auxiliary agents.
2. The nano-deoxidant composition according to claim 1, wherein: the auxiliary agent adopts a conventional auxiliary agent and comprises 1-25 parts of surface treating agent and 1-5 parts of binder.
3. The nano-deoxidant composition according to claim 2, wherein: the surface treating agent is polyethylene diketone, polyethylene glycol or polycarbonate; the binder is polyethylene glycol.
4. The method for synthesizing a nano deoxidizer of claim 1 is characterized by comprising the steps of:
1) ordinary manganese carbonate is used as a raw material, and is subjected to acid dissolution to synthesize nano MnCO3；MnCO3The purity is more than or equal to 99 percent, the surface of the powder is organically treated by a surface treating agent, and the particle size distribution D90 is less than or equal to 100 nm;
2) nano MnCO3Adding ZnOand Cu2O and adhesive, grinding, rolling ball and roasting to obtain the product.
5. The method for synthesizing a nano deoxidizer of claim 4, comprising the steps of: in the step 1), the manganese carbonate is dissolved by hydrochloric acid to generate MnCl2After, with NH4HCO3And (3) carrying out titration reaction, wherein the titration speeds of the two materials are the same, the molar ratio is 1: 2, stirring is carried out during the reaction, the temperature is 40-100 ℃, and the constant temperature time is 1-4 hours.
6. The method for synthesizing a nano deoxidizer of claim 4, comprising the steps of: in the step 2), the materials are mixed in a stirring mixer, processed into balls by using a roller granulator, and then roasted at the temperature of 300-450 ℃ for 1-4 hours to obtain black pellets with the shape of phi 3-5 mm.
7. The method for synthesizing a nano deoxidizer of claim 4, wherein the deoxidizer contains an active component Mn in an amount of 22 to 44% by weight.
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| SU1298250A1 (en) * | 1985-11-22 | 1987-03-23 | Череповецкий Металлургический Комбинат Им.50-Летия Ссср | Method for deoxidation of low-carbon steel |
| CN1077446C (en) * | 1998-09-02 | 2002-01-09 | 中国科学院大连化学物理研究所 | High-activity deoxidant and preparing process thereof |
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Commission number: 4W101978 Conclusion of examination: Claim No. 200410082865.3 of the invention No. 1 is invalid and the patent is maintained on the basis of the claim 2-5 submitted by the patent holder in February 7, 2013. Decision date of declaring invalidation: 20131024 Decision number of declaring invalidation: 21472 Denomination of invention: Nano-deoxidant composition and its synthesis method Granted publication date: 20080109 Patentee: Dalian Samat Chemicals Co.,Ltd. |