CN102850166B - Olefin deoxygenation agent, its preparation method, and olefin deoxygenation method using the same - Google Patents
Olefin deoxygenation agent, its preparation method, and olefin deoxygenation method using the same Download PDFInfo
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- CN102850166B CN102850166B CN201110184605.7A CN201110184605A CN102850166B CN 102850166 B CN102850166 B CN 102850166B CN 201110184605 A CN201110184605 A CN 201110184605A CN 102850166 B CN102850166 B CN 102850166B
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Abstract
The invention discloses an olefin deoxygenation agent, its preparation method, and olefin deoxygenation method using the same. The preparation method includes (by weight parts) (1) mixing manganese source (as Mn3O4) 100 and titania nanoparticle 58-100 to obtain a mixture; (2) calcining; (3) kneading the calcined mixture and a silver compound (as Ag2O) aqueous solution 8-35, and forming; (4) aging and drying; and (5) calcining. The second calcining temperature is lower than the first calcining temperature. The inventive olefin deoxygenation agent has high room-temperature deoxygenation capacity up to 27.1 mL/g, deoxygenation depth lower than 0.01 ppm, low reduction temperature, and wide applicability in industrial production.
Description
Technical field
The alkene reductor that the present invention relates to a kind of preparation method of alkene reductor and made by this preparation method and the application of this alkene reductor and alkene method of deoxidation.
Background technology
Alkene is important basic organic chemical raw material.Therein ethylene and propylene are produced the main raw material of macromolecule polymeric material especially.Along with developing rapidly of polyethylene and polypropylene technology, the sequential use such as various new and effective polyethylene, polypropylene catalyst and metallocene catalyst are in industrial production.In order to avoid, the efficient polyolefin catalyst of this class is poisoning, inactivation and improving the quality of products, and the foreign matter content of the ethene for polymerization and propylene feedstocks is had to strict restriction.According to ethene and propylene feedstocks national standard, in qualified polymer grade ethylene, propylene, oxygen level is≤5ppm (5 * 10
-6v/V, below identical), can not meet the requirement of novel polymeric technique, need in polymerization process, to micro amount of oxygen in ethene and propylene, further remove, oxygen level is purified to≤0.1ppm.Therefore, to be applied to the deep purifying high efficiency deoxidiser of ethene and propylene gas-phase polymerization process be necessary in research and development.
The micro amount of oxygen of applying in Patents document and industrial production purifies adopt more and is unworthy of hydrogen deoxidization technique.Being unworthy of hydrogen deoxidation is to utilize the micro amount of oxygen in medium that the reductor of reduction-state is oxidized, and generates the decontamination effect improving that high oxide reaches deoxidation.Such reductor, because deoxidation finite capacity, for preventing frequent reducing/regenerating, affects normal production, is mainly applicable to oxygen level in gas and is less than 50ppm, is particularly less than the deoxidization technique of 10ppm.
CN1246383A discloses a kind of hydrogen reductor that is unworthy of, and wherein Mn content is 24～44 % by weight, and support carrier is high-alumina cement, diatomite or Al
2o
3.Deoxidation capacity when this reductor is used for ethene deoxidation is only 5.3ml/g.
CN1110249A discloses a kind of loading type reductor, utilizes pickling process at Al
2o
3load Mn (NO on carrier
3)
2, Ni (NO
3)
2with in alkaline-earth metal one or more oxide compound and prepare and be unworthy of hydrogen reductor.This reductor is for nitrogen deoxidation, and the deoxidation capacity under room temperature is 16.2ml/g.
CN1342516A discloses the reductor that a kind of bimetallic oxide MnO and CuO are active constituent, and adds Al
2o
3carrier machine-shaping, this reductor is for ethene deoxidation, and under room temperature, deoxidation capacity is 10ml/g.
CN1955150A discloses a kind of with Mn
3o
4for active ingredient, add the reductor of accelerative activator alkaline earth metal oxide and aluminum oxide, for the purification of the alkene micro amount of oxygen such as ethene and propylene, under room temperature, deoxidation capacity is 7.6ml/g.
CN101165030A discloses a kind of Mn-Ag double activated component reductor, reduction temperature can be reduced.But, the mixture carrier of the calcium aluminate using or calcium aluminate and ca aluminosilicate need to be at 1200 ℃～1650 ℃ temperature lower calcination 3～8h, then pulverize, sieve, the production cost of reductor is higher, and the specific surface area of carrier is low, this reductor is for ethene deoxidation, and under room temperature, deoxidation capacity is 10.9ml/g.
As can be seen here, under alkene reductor room temperature prepared by prior art, deoxidation capacity is on the low side, work-ing life is short, in order to extend the work-ing life of alkene reductor, must improve deoxygenation temperature, and result brings polyolefine plant energy consumption to increase.
Summary of the invention
The object of the invention is, in order to overcome the defect that under existing alkene reductor room temperature (25 ℃), deoxidation capacity is low, work-ing life is short, provides a kind of new alkene reductor and its preparation method and application and alkene method of deoxidation.
The present inventor surprisingly finds under study for action, adopts nano level TiO
2as support material, prepare alkene reductor, can greatly improve the deoxidation capacity under alkene reductor room temperature, and increase the service life, and can reach the darker deoxidation degree of depth.
Therefore, to achieve these goals, on the one hand, the invention provides a kind of preparation method of alkene reductor, said method comprising the steps of:
(1) by manganese source and nano level TiO
2mix and obtain mixture, respectively with Mn
3o
4with nano level TiO
2meter, the manganese source based on 100 weight parts, nano level TiO
2consumption be 58-100 weight part, described manganese source is Mn
3o
4and/or can access Mn after roasting
3o
4the compound of manganese;
(2) mixture step (1) being obtained carries out the first roasting;
(3), by the aqueous solution incipient impregnation of the product after step (2) roasting and silver-colored compound, then mediate, moulding, respectively with Mn
3o
4and Ag
2o meter, the manganese source based on 100 weight parts, the aqueous solution of the compound of silver is 8-35 weight part, the compound of described silver is can decompose and obtain Ag after roasting
2the compound of the water miscible silver of O;
(4) product of step (3) moulding is carried out to burin-in process, then the solid after burin-in process is dried;
(5) the dried product of step (4) is carried out to the second roasting, the temperature of described the second roasting is lower than the temperature of described the first roasting, and the temperature of described the first roasting can make the decomposition of described manganese source obtain Mn
3o
4, the temperature of described the second roasting can make the compound decomposition of described silver obtain Ag
2o.
On the other hand, the invention provides a kind of alkene reductor, described alkene reductor is made by method as above.
The third aspect, the invention provides the application of a kind of alkene reductor as above in alkene deoxidation.
Fourth aspect, the invention provides a kind of alkene method of deoxidation, described method comprises with the reducing gas that contains hydrogen reduces to above-mentioned alkene reductor, then, under alkene deoxygenation conditions, alkene is carried out to gas phase deoxidation by the alkene reductor after reducing.
Alkene reductor of the present invention adopts nano level TiO
2make carrier, the deoxidation capacity under room temperature is high, and when preparation adopt a minute one-step baking, can make manganese source decompose and obtain Mn under comparatively high temps
3o
4, silver-colored compound is decomposed at a lower temperature and obtains Ag
2o, avoided Ag sintering, further improved deoxidation capacity, deoxidation capacity can reach 27.1ml/g, much larger than the deoxidation capacity under existing alkene reductor room temperature, therefore under identical deoxygenation conditions, be also correspondingly longer than the work-ing life of existing alkene reductor the work-ing life of alkene reductor of the present invention; The deoxidation degree of depth is less than 0.01ppm, is less than 0.05ppm has reduced by five times than prior art level; Reduction temperature is low, reducible at 150～160 ℃ of temperature, and the reductor reduction temperature that can provide with existing polyolefin device is consistent, and therefore not needing to carry out plant modification can directly use.Alkene reductor provided by the invention has successfully been realized efficient deoxidation under room temperature, according to contriver, calculate, produce per year 300,000 tons of polyethylene devices room temperature not under heating condition deoxidation than deoxidation at 100 ℃, can save every year units up to a million, saved the energy, reduced the discharge of greenhouse gases, alkene reductor of the present invention can be widely used in industrial production.
Other features and advantages of the present invention partly in detail are described the embodiment subsequently.
Embodiment
Below the specific embodiment of the present invention is elaborated.Should be understood that, embodiment described herein only, for description and interpretation the present invention, is not limited to the present invention.
On the one hand, the invention provides a kind of preparation method of alkene reductor, said method comprising the steps of:
(1) by manganese source and nano level TiO
2mix and obtain mixture, respectively with Mn
3o
4with nano level TiO
2meter, the manganese source based on 100 weight parts, nano level TiO
2consumption be 58-100 weight part, described manganese source is Mn
3o
4and/or can access Mn after roasting
3o
4the compound of manganese;
(2) mixture step (1) being obtained carries out the first roasting;
(3), by the aqueous solution incipient impregnation of the product after step (2) roasting and silver-colored compound, then mediate, moulding, respectively with Mn
3o
4and Ag
2o meter, the manganese source based on 100 weight parts, the aqueous solution of the compound of silver is 8-35 weight part, the compound of described silver is can decompose and obtain Ag after roasting
2the compound of the water miscible silver of O;
(4) product of step (3) moulding is carried out to burin-in process, then the solid after burin-in process is dried;
(5) the dried product of step (4) is carried out to the second roasting, the temperature of described the second roasting is lower than the temperature of described the first roasting, and the temperature of described the first roasting can make the decomposition of described manganese source obtain Mn
3o
4, the temperature of described the second roasting can make the compound decomposition of described silver obtain Ag
2o.
Room temperature in the present invention refers to 25 ℃.Ppm refers to volumetric concentration.
Nano level TiO
2type have Detitanium-ore-type, rutile-type and brookite type three types, preferably adopt nano level Detitanium-ore-type and/or nm-class rutile-type TiO
2as support material, prepare alkene reductor, further preferably adopt nano level Detitanium-ore-type TiO
2as support material, prepare alkene reductor.Nano level TiO in the present invention
2refer to average particle size range and in nanometer scale, do not reach the TiO of micron number magnitude
2, i.e. the TiO of median size below 1 μ m
2; Non-nano level TiO
2refer to average particle size range not in nanometer scale, the TiO more than nanometer scale
2.
Median size in the present invention refers to volume average particle size, adopts transmission electron microscope to record.
According to the present invention, although adopt nano level TiO
2as the carrier of alkene reductor, prepare alkene reductor, and the consumption in manganese source, TiO
2consumption and concentration and the consumption of the aqueous solution of the compound of silver make with Mn
3o
4, nano level TiO
2and Ag
2o meter, the manganese source based on 100 weight parts, nano level TiO
2consumption be 58-100 weight part, the aqueous solution of compound of silver is 8-35 weight part, can reach object of the present invention, but under preferable case, nano level TiO
2median size be 5-50nm, can further improve the deoxidation capacity under the alkene reductor room temperature that the inventive method makes, further extend the work-ing life under alkene reductor room temperature; Under further preferable case, nano level TiO
2median size be 5-20nm, can further improve the deoxidation capacity under the alkene reductor room temperature that the inventive method makes, further extend the work-ing life under alkene reductor room temperature.
Nano level TiO
2specific surface area be preferably 30-200m
2/ g, more preferably 100-200m
2/ g.
As long as the compound of manganese can access Mn after meeting roasting
3o
4; it can be the compound of the thinkable various manganese of those skilled in the art; be preferably selected from least one in the group being formed by manganous carbonate, manganese acetate, formic acid manganese, manganous oxalate, manganese acetylacetonate, manganous phosphate, Manganous chloride tetrahydrate, manganous nitrate, Manganse Dioxide, manganous sulfate and manganous hydroxide; more preferably select at least one in the group that free manganous carbonate, manganous oxalate, manganese acetate and formic acid manganese forms, more preferably manganous carbonate.
As long as the compound of silver is for decomposing and obtain Ag after roasting
2the compound of the water miscible silver of O, can, by the compound of the thinkable various silver of those skilled in the art, be preferably Silver Nitrate.
The consumption of preparation method's Raw of alkene reductor provided by the invention, i.e. manganese source and nano level TiO
2consumption and concentration and the consumption of the aqueous solution of the compound of silver make respectively with Mn
3o
4, nano level TiO
2and Ag
2o meter, the manganese source based on 100 weight parts, nano level TiO
2for 58-100 weight part, the aqueous solution of the compound of silver is 8-35 weight part, is preferably the manganese source based on 100 weight parts, nano level TiO
2consumption be 58-85 weight part, the aqueous solution of compound of silver is 15-35 weight part, the manganese source based on 100 weight parts more preferably, nano level TiO
2for 58-70 weight part, the aqueous solution of the compound of silver is 20-35 weight part.
By manganese source and nano level TiO
2mix and obtain mixture, the method mixing, without particular requirement, can adopt the conventional the whole bag of tricks in this area, for example can be by manganese source and nano level TiO
2putting into cone-type mixer mixes.
The first roasting is to obtain Mn for manganese source is decomposed
3o
4, the condition optimization of roasting is roasting 2-10h at 400-550 ℃, more preferably roasting 2-10h at 450-500 ℃.
By the aqueous solution incipient impregnation of the product after step (2) roasting and silver-colored compound, then mediate, moulding, so that manganese source, nano level TiO
2even with the aqueous solution of silver-colored compound.For the shape after the method for incipient impregnation and kneading, moulding and kneading, moulding without particular requirement, for example can in the product after step (2) roasting, add the aqueous solution of silver-colored compound to carry out incipient impregnation, then with banded extruder, be prepared into strip segment, also the product after step (2) roasting can be joined in coater, the aqueous solution that sprays into silver-colored compound carries out incipient impregnation, is then rolled onto spherical.
In the present invention, the product of step (3) moulding is carried out to burin-in process and be preferably the airtight placement of product of step (3) moulding, airtight being placed under room temperature normal pressure, the time of airtight placement is preferably 12-72h, more preferably 24-60h.For dry, without particular requirement, can adopt the conventional the whole bag of tricks adopting in this area to be dried, dry condition optimization is dry 5-12h at 80-150 ℃, more preferably dry 8-12h at 100-140 ℃.
The second roasting is in order to make silver-colored compound decomposition obtain Ag
2o, the condition optimization of roasting carries out at 200-300 ℃, more preferably roasting 1-5h at 200-300 ℃.
On the other hand, the invention provides a kind of alkene reductor of being prepared by aforesaid method.The mean pore size of alkene reductor is preferably 10-50nm, and specific surface area is preferably 50-250m
2/ g.
The alkene reductor of being prepared by the inventive method, through XRD analysis, includes stronger Mn
3o
4characteristic diffraction peak, TiO
2characteristic peak and weak Ag
2o characteristic peak.
Active constituent before alkene reductor prepared by the inventive method is used in reductor product is Ag
2o and Mn
3o
4, it should be appreciated by those skilled in the art that while using and need scene that this active ingredient is reduced into active constituent Ag and the MnO with deoxidizing capacity.Equally, the alkene reductor after reduction is after deoxidation is after a while used, and the Ag of lower valency and MnO can be oxidized to the Ag of high valence state
2o and Mn
3o
4.When oxygen level is greater than and requires index after alkene reductor complete deactivation or deoxidation, need reducing/regenerating reductor again, reductor of the present invention can on-the-spot reducing/regenerating, reuses.The active ingredient under room temperature with deoxy activity is mainly the Ag of high dispersing.
The concrete reductive condition of alkene reductor is preferably: logical temperature is hydrogen or hydrogen and the N of 130-160 ℃
2the on-the-spot reduction of mixed gas, hydrogen or hydrogen and N
2the volume space velocity 50-2000h of mixed gas
-1, the recovery time is 5-24h; More preferably: logical temperature is hydrogen and the N that the hydrogeneous volume fraction of 150～160 ℃ is 0.5-10%
2the on-the-spot reduction of mixed gas, hydrogen and N
2the volume space velocity of mixed gas be 50-1000h
-1, the recovery time is 10-15h.
The third aspect, the invention provides the application of above-mentioned alkene reductor in alkene deoxidation.For concrete application, have no special requirements, can, for the application mode of this area routine, not repeat them here.
Fourth aspect, the invention provides a kind of alkene method of deoxidation, described method comprises with the reducing gas that contains hydrogen reduces to above-mentioned alkene reductor, then, under alkene deoxygenation conditions, alkene is carried out to gas phase deoxidation by the alkene reductor after reducing.
For concrete alkene method of deoxidation, have no special requirements, can adopt the conventional the whole bag of tricks adopting in this area, for example can in fixed-bed reactor, the alkene that contains 2-5 carbon atom be carried out to gas phase deoxidation by the alkene reductor through reduction, in alkene, oxygen level is 1-100ppm, and alkene volume space velocity is 100-3000h
-1, the service temperature of fixed-bed reactor is 20-100 ℃, pressure is 0.1-10MPa.More preferably in fixed-bed reactor, the alkene that contains 2-4 carbon atom is carried out to gas phase deoxidation by the alkene reductor through reduction, in alkene, oxygen level is 1-5ppm, and alkene volume space velocity is 500-2000h
-1, the service temperature of fixed-bed reactor is 20-30 ℃, pressure is 0.1-5MPa.The alkene that carries out deoxidation is ethene or propylene more preferably.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characterictic described in above-mentioned embodiment, in reconcilable situation, can combine by any suitable mode, for fear of unnecessary repetition, the present invention is to the explanation no longer separately of various possible array modes.
In addition, between various embodiment of the present invention, also can carry out arbitrary combination, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Embodiment
The present invention is further illustrated for following embodiment, but therefore do not limit the present invention.
In following embodiment and comparative example, the measuring method of alkene reductor deoxidation capacity and the deoxidation degree of depth is as follows: get 50ml alkene reductor and pack in the stainless steel reactor of Φ 25mm, at 150 ℃, pass into hydrogen volume mark and be 1% nitrogen, at volume space velocity 200h
-1under condition, reduce after 12h and stop passing into.After cooling, at pressure 0.4MPa, at 25 ℃ of temperature, pass into ethene, volume of ethylene air speed is 1500h
-1, entrance oxygen level 1000ppm.After system brings into operation, the concentration of residual oxygen after observation deoxidation in ethene, the concentration of residual oxygen after discovery deoxidation in ethene is less than 0.01ppm all the time, and the concentration of residual oxygen after deoxidation in ethene stops experiment while being greater than 0.01ppm.The present invention is defined as after deoxidation concentration of residual oxygen (ppm) in alkene by the deoxidation degree of depth under alkene reductor room temperature; The oxygen volume that deoxidation capacity definition is removed when the deoxidation degree of depth is less than 0.01ppm (the milliliter number of correspondence under standard state), divided by the quality of reductor, measure unit is ml/g.
In following embodiment and comparative example, TiO
2be purchased from Xuancheng Jingrui New Material Co., Ltd..
Embodiment 1
This embodiment is used for illustrating the preparation method of alkene reductor provided by the invention.
By MnCO
3with median size be that 9.8nm, specific surface area are 160m
2the Detitanium-ore-type TiO of/g
2mix.MnCO
3and TiO
2consumption make respectively with Mn
3o
4and TiO
2meter, the MnCO based on 1000g
3, TiO
2for 650g, then by mixing the mixture obtaining, at 480 ℃, carry out the first roasting 5h.
In product after the first roasting, add AgNO
3solution carries out incipient impregnation, AgNO
3concentration and the consumption of solution make with Mn
3o
4and Ag
2o meter, the MnCO based on 1000g
3, AgNO
3solution is 300g, fully mediates, and is prepared into the strip segment of the long 5mm of diameter of phi 3mm with banded extruder, and then airtight placement 48h is then dried 8h at 120 ℃, then at 250 ℃, carries out the second roasting 3h, is prepared into alkene reductor.Record the deoxidation capacity of the alkene reductor making and the deoxidation degree of depth in Table 1.
Embodiment 2
This embodiment is used for illustrating the preparation method of alkene reductor provided by the invention.
By MnCO
3with median size be that 5nm, specific surface area are 200m
2the Detitanium-ore-type TiO of/g
2mix.MnCO
3and TiO
2consumption make respectively with Mn
3o
4and TiO
2meter, the MnCO based on 1000g
3, TiO
2for 580g, then by mixing the mixture obtaining, at 500 ℃, carry out the first roasting 2h.
Product after the first roasting is joined in coater, spray into AgNO
3solution carries out incipient impregnation, AgNO
3concentration and the consumption of solution make with Mn
3o
4and Ag
2o meter, the MnCO based on 1000g
3, AgNO
3solution is 350g, is rolled onto the spherical of Φ 3mm, and then airtight placement 60h is then dried 5h at 140 ℃, then at 300 ℃, carries out the second roasting 1h, is prepared into alkene reductor.Record the deoxidation capacity of the alkene reductor making and the deoxidation degree of depth in Table 1.
Embodiment 3
This embodiment is used for illustrating the preparation method of alkene reductor provided by the invention.
By MnCO
3with median size be that 20nm, specific surface area are 100m
2the Detitanium-ore-type TiO of/g
2mix.MnCO
3and TiO
2consumption make respectively with Mn
3o
4and TiO
2meter, the MnCO based on 1000g
3, TiO
2for 700g, then by mixing the mixture obtaining, at 450 ℃, carry out the first roasting 10h.
In product after the first roasting, add AgNO
3solution carries out incipient impregnation, AgNO
3concentration and the consumption of solution make with Mn
3o
4and Ag
2o meter, the MnCO based on 1000g
3, AgNO
3solution is 200g, fully mediates, and is prepared into the strip segment of the long 5mm of diameter of phi 3mm with banded extruder, and then airtight placement 24h is then dried 12h at 100 ℃, then at 200 ℃, carries out the second roasting 5h, is prepared into alkene reductor.Record the deoxidation capacity of the alkene reductor making and the deoxidation degree of depth in Table 1.
Embodiment 4
According to the method for embodiment 1, prepare alkene reductor, different, Detitanium-ore-type TiO
2median size be 40nm, record the deoxidation capacity of the alkene reductor making and the deoxidation degree of depth in Table 1.
Embodiment 5
According to the method for embodiment 1, prepare alkene reductor, different, Detitanium-ore-type TiO
2specific surface area be 40m
2/ g, records the deoxidation capacity of the alkene reductor making and the deoxidation degree of depth in Table 1.
Embodiment 6
According to the method for embodiment 1, prepare alkene reductor, different, AgNO
3concentration and the consumption of solution make with Mn
3o
4and Ag
2o meter, the MnCO based on 1000g
3, AgNO
3solution is 100g, records the deoxidation capacity of the alkene reductor making and the deoxidation degree of depth in Table 1.
Embodiment 7
According to the method for embodiment 1, prepare alkene reductor, different, with Mn
3o
4, TiO
2and Ag
2o meter, MnCO
3consumption be 900g, TiO
2consumption and AgNO
3concentration and the consumption of solution are constant, record the deoxidation capacity of the alkene reductor making and the deoxidation degree of depth in Table 1.
Embodiment 8
According to the method for embodiment 1, prepare alkene reductor, different, TiO
2for rutile TiO
2, median size is that 10nm, specific surface area are 165m
2/ g, records the deoxidation capacity of the alkene reductor making and the deoxidation degree of depth in Table 1.
Comparative example 1
According to the method for embodiment 1, prepare alkene reductor, different, TiO
2for Detitanium-ore-type non-nano level TiO
2, median size is 2 μ m, specific surface area is 150m
2/ g, records the deoxidation capacity of the alkene reductor making and the deoxidation degree of depth in Table 1.
Comparative example 2
According to the method for embodiment 1, prepare alkene reductor, different, by median size, be that 20 μ m, specific surface area are 300m
2γ-Al of/g
2o
3alternative median size is that 9.8nm, specific surface area are 160m
2the Detitanium-ore-type TiO of/g
2, record the deoxidation capacity of the alkene reductor making and the deoxidation degree of depth in Table 1.
Comparative example 3
By MnCO
3with median size be that 9.8nm, specific surface area are 160m
2the Detitanium-ore-type TiO of/g
2mix.MnCO
3and TiO
2consumption make respectively with Mn
3o
4and TiO
2meter, the MnCO based on 1000g
3, TiO
2for 650g, in the blend composition after mixing, add AgNO
3solution carries out incipient impregnation, AgNO
3concentration and the consumption of solution make with Mn
3o
4and Ag
2o meter, the MnCO based on 1000g
3, AgNO
3solution is 300g, fully mediates, and is prepared into the strip segment of the long 5mm of diameter of phi 3mm with banded extruder, and then airtight placement 48h is then dried 10h at 120 ℃, and then roasting 5h at 480 ℃, is prepared into alkene reductor.Record the deoxidation capacity of the alkene reductor making and the deoxidation degree of depth in Table 1.
Table 1 embodiment and comparative example experimental result
| Embodiment | Deoxidation capacity (ml/g) | The deoxidation degree of depth (ppm) |
| 1 | 25.9 | 0.008 |
| 2 | 27.1 | 0.008 |
| 3 | 23.8 | 0.007 |
| 4 | 22.5 | 0.007 |
| 5 | 21.4 | 0.008 |
| 6 | 20.8 | 0.009 |
| 7 | 24.3 | 0.009 |
| 8 | 21.6 | 0.008 |
| Comparative example 1 | 14.9 | 0.031 |
| Comparative example 2 | 10.8 | 0.042 |
| Comparative example 3 | 24.5 | 0.008 |
Embodiment 1 and comparative example 1 are compared and can be found out, non-nano level TiO
2, the deoxidation capacity of the alkene reductor of making obviously reduces.Embodiment 1 and comparative example 2 are compared and can be found out, adopt Al
2o
3the alkene reductor of making alkene reductor carrier is nothing like employing TiO
2the deoxidation effect of alkene reductor of making alkene reductor carrier is good; Embodiment 1 and comparative example 3 are compared and can be found out, by MnCO
3under comparatively high temps, carry out the first Roasting Decomposition and become Mn
3o
4after again with AgNO
3solution incipient impregnation, then carries out at a lower temperature the second roasting and makes AgNO
3resolve into Ag
2the alkene reductor that O obtains, compared with by MnCO
3with AgNO
3the deoxidation effect of the alkene reductor that after solution incipient impregnation, roasting obtains under comparatively high temps is together good, and theoretical derivation may be due to MnCO
3resolve into Mn completely
3o
4need to be in more than 400 ℃ roasting, and be easy to be partially sintered at more than 400 ℃ silver, thereby the silver-colored dispersity in the alkene reductor that makes to make reduces and causes.
Embodiment 1 and embodiment 4 compare and can find out, nano level Detitanium-ore-type TiO
2median size less, the deoxidation capacity of the alkene reductor of making is higher, theoretical derivation may be due to the little TiO of median size
2can be with and conduction band between band-gap energy high, its hole and electronics have very strong redox ability; Embodiment 1 and embodiment 5 compare and can find out, nano level Detitanium-ore-type TiO
2specific surface area larger, the deoxidation capacity of the alkene reductor of making is higher; Embodiment 1 and embodiment 6 compare and can find out, Ag in the alkene reductor making
2the content of O is higher, and the deoxidation capacity of alkene reductor is higher, and Ag
2the content of O has considerable influence to the deoxidation capacity of alkene reductor, visible Ag
2o is the main active ingredient in alkene reductor; Embodiment 1 and embodiment 7 compare and can find out, Mn in the alkene reductor making
3o
4content higher, the deoxidation capacity of the alkene reductor of making is higher, but Mn
3o
4content little to the deoxidation capacity impact of alkene reductor, visible Mn
3o
4for the less important activeconstituents in alkene reductor, theoretical derivation may be because high dispersing is at TiO
2than MnO at room temperature there is oxidizing reaction in the micro amount of oxygen more easily and in raw material to Ag on carrier.Embodiment 1 and embodiment 8 are compared and can be found out, rutile TiO
2the alkene reductor making is not as Detitanium-ore-type TiO
2the deoxidation effect of the alkene reductor making is good.
Alkene reductor of the present invention adopts nano level TiO
2make carrier, the deoxidation capacity under room temperature is high, and when preparation adopt a minute one-step baking, can make manganese source decompose and obtain Mn under comparatively high temps
3o
4, silver-colored compound is decomposed at a lower temperature and obtains Ag
2o, avoided Ag sintering, further improved deoxidation capacity, deoxidation capacity can reach 27.1ml/g, much larger than the deoxidation capacity under existing alkene reductor room temperature, therefore under identical deoxygenation conditions, be also correspondingly longer than the work-ing life of existing alkene reductor the work-ing life of alkene reductor of the present invention; The deoxidation degree of depth is less than 0.01ppm, is less than 0.05ppm has reduced by five times than prior art level; Reduction temperature is low, reducible at 150～160 ℃ of temperature, and the reductor reduction temperature that can provide with existing polyolefin device is consistent, and therefore not needing to carry out plant modification can directly use.Alkene reductor provided by the invention has successfully been realized efficient deoxidation under room temperature, has saved the energy, has reduced the discharge of greenhouse gases, can be widely used in industrial production.
Claims (13)
1. a preparation method for alkene reductor, said method comprising the steps of:
(1) by manganese source and nano level TiO
2mix and obtain mixture, respectively with Mn
3o
4with nano level TiO
2meter, the manganese source based on 100 weight parts, nano level TiO
2consumption be 58-100 weight part, described manganese source is Mn
3o
4and/or can access Mn after roasting
3o
4the compound of manganese;
(2) mixture step (1) being obtained carries out the first roasting;
(3), by the aqueous solution incipient impregnation of the product after step (2) roasting and silver-colored compound, then mediate, moulding, respectively with Mn
3o
4and Ag
2o meter, the manganese source based on 100 weight parts, the aqueous solution of the compound of silver is 8-35 weight part, the compound of described silver is can decompose and obtain Ag after roasting
2the compound of the water miscible silver of O;
(4) product of step (3) moulding is carried out to burin-in process, then the solid after burin-in process is dried;
(5) the dried product of step (4) is carried out to the second roasting, the temperature of described the second roasting is lower than the temperature of described the first roasting, and the temperature of described the first roasting can make the decomposition of described manganese source obtain Mn
3o
4, the temperature of described the second roasting can make the compound decomposition of described silver obtain Ag
2o;
Wherein, the burin-in process in described step (4) is for to carry out airtight placement by the product of step (3) moulding, and the temperature of described the first roasting is 400-550 ℃, and the temperature of described the second roasting is 200-300 ℃, described nano level TiO
2median size be 5-50nm, described nano level TiO
2specific surface area be 30-200m
2/ g.
2. method according to claim 1, wherein, described nano level TiO
2median size be 5-20nm.
3. method according to claim 1, wherein, described nano level TiO
2specific surface area be 100-200m
2/ g.
4. method according to claim 1, wherein, described nano level TiO
2for nano level Detitanium-ore-type TiO
2.
5. method according to claim 1, wherein, the compound of described manganese is at least one that select in the group that free manganous carbonate, manganese acetate, formic acid manganese, manganous oxalate, manganese acetylacetonate, manganous phosphate, Manganous chloride tetrahydrate, manganous nitrate, Manganse Dioxide, manganous sulfate and manganous hydroxide form.
6. method according to claim 5, wherein, the compound of described manganese is at least one that select in the group that free manganous carbonate, manganous oxalate, manganese acetate and formic acid manganese forms.
7. method according to claim 6, wherein, the compound of described manganese is manganous carbonate.
8. method according to claim 1, wherein, the compound of described silver is Silver Nitrate.
9. an alkene reductor, is characterized in that, described alkene reductor method described in any one in claim 1-8 is made.
10. alkene reductor according to claim 9, wherein, the mean pore size of described alkene reductor is 10-50nm.
11. alkene reductors according to claim 9, wherein, the specific surface area of described alkene reductor is 50-250m
2/ g.
The application in alkene deoxidation of 12. 1 kinds of alkene reductors as described in any one in claim 9-11.
13. 1 kinds of alkene method of deoxidations, described method comprises with the reducing gas that contains hydrogen reduces to the alkene reductor described in any one in claim 9-11, then under alkene deoxygenation conditions, alkene is carried out to gas phase deoxidation by the alkene reductor after reducing.
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| CN1785477A (en) * | 2004-12-06 | 2006-06-14 | 大连圣迈化学有限公司 | Nano-deoxidant composition and its synthesis method |
| CN101165030A (en) * | 2006-10-20 | 2008-04-23 | 中国石油化工股份有限公司 | Mn-Ag double active components desoxidant, preparation method and application thereof |
| CN101328104A (en) * | 2007-06-21 | 2008-12-24 | 中国石油化工股份有限公司 | Alkene liquid phase deoxidizing agent, preparation and application thereof |
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| CN1785477A (en) * | 2004-12-06 | 2006-06-14 | 大连圣迈化学有限公司 | Nano-deoxidant composition and its synthesis method |
| CN101165030A (en) * | 2006-10-20 | 2008-04-23 | 中国石油化工股份有限公司 | Mn-Ag double active components desoxidant, preparation method and application thereof |
| CN101328104A (en) * | 2007-06-21 | 2008-12-24 | 中国石油化工股份有限公司 | Alkene liquid phase deoxidizing agent, preparation and application thereof |
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