CN102850164A - 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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- CN102850164A CN102850164A CN2011101845942A CN201110184594A CN102850164A CN 102850164 A CN102850164 A CN 102850164A CN 2011101845942 A CN2011101845942 A CN 2011101845942A CN 201110184594 A CN201110184594 A CN 201110184594A CN 102850164 A CN102850164 A CN 102850164A
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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, modified titania nanoparticle 58-100 and binder 1.5-25 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 inventive olefin deoxygenation agent has high room-temperature deoxygenation capacity, high mechanical crushing strength, low deoxygenation depth, low reduction temperature, and wide applicability in industrial production.
Description
Technical field
The present invention relates to application and the alkene method of deoxidation of a kind of preparation method of alkene reductor and the alkene reductor that is made by this preparation method and this alkene reductor.
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.For avoiding the efficient polyolefin catalyst poisoning of this class, inactivation and improving the quality of products, to for the ethene of polymerization and the foreign matter content of propylene feedstocks strict restriction being arranged.According to ethene and propylene feedstocks national standard, oxygen level is≤5ppm (5 * 10 in qualified polymer grade ethylene, the propylene
-6V/V, below identical), can not satisfy the requirement of novel polymeric technique, need in polymerization process, further remove micro amount of oxygen in ethene and the propylene, 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 using in Patents document and the industrial production purifies adopt more and is unworthy of the hydrogen deoxidization technique.Be unworthy of the hydrogen deoxidation and be utilizing micro amount of oxygen in the medium with the reductor oxidation of reduction-state, generate the decontamination effect improving that high oxide reaches deoxidation.Such reductor for preventing frequent reducing/regenerating, affects normal production because the deoxidation finite capacity, mainly is applicable in the gas oxygen level less than 50ppm, 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 the support carrier is high-alumina cement, diatomite or Al
2O
3Deoxidation capacity when this reductor is used for the ethene deoxidation only is 5.3ml/g.
CN1110249A discloses a kind of loading type reductor, utilizes pickling process at Al
2O
3Load Mn (NO on the carrier
3)
2, Ni (NO
3)
2With in the alkaline-earth metal one or more oxide compound and prepare and be unworthy of the hydrogen reductor.This reductor is used for the nitrogen deoxidation, and the deoxidation capacity under the room temperature is 16.2ml/g.
CN1342516A discloses a kind of bimetallic oxide MnO and CuO is the reductor of active constituent, and adds Al
2O
3Carrier machine-shaping, this reductor is used for the ethene deoxidation, and the deoxidation capacity is 10ml/g under the room temperature.
CN1955150A discloses a kind of with Mn
3O
4Be active ingredient, add the reductor of accelerative activator alkaline earth metal oxide and aluminum oxide, be used for the purification of the alkene micro amount of oxygen such as ethene and propylene, the deoxidation capacity is 7.6ml/g under the room temperature.
CN101165030A discloses a kind of Mn-Ag double activated component reductor, reduction temperature can be reduced.But, the mixture carrier of employed calcium aluminate 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 used for the ethene deoxidation, and the deoxidation capacity is 10.9ml/g under the room temperature.
This shows, the deoxidation capacity is on the low side under the alkene reductor room temperature of prior art preparation, work-ing life is short, and in order to improve the deoxygenation temperature work-ing life that prolongs the alkene reductor, the result brings the polyolefine plant energy consumption to increase.
Summary of the invention
The objective of the invention is provides a kind of new alkene reductor and its preparation method and application and alkene method of deoxidation in order to overcome the lower defective that the deoxidation capacity is low, work-ing life is short of existing alkene reductor room temperature (25 ℃).
The present inventor is unexpected the discovery under study for action, adopts nano level TiO
2Make carrier, can greatly improve the deoxidation capacity under the alkene reductor room temperature, and increase the service life, and can reach the darker deoxidation degree of depth, adopt the nano level TiO of modification by alkali metal
2Make carrier, can further improve the deoxidation capacity under the alkene reductor room temperature, increase the service life.
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) with the nano level TiO of manganese source and alkalimetal oxide and/or alkali metal hydroxide modification
2Mix with tackiness agent and to obtain mixture, respectively with Mn
3O
4, modification nano level TiO
2With the tackiness agent meter, based on the manganese source of 100 weight parts, the nano level TiO of modification
2Consumption be the 58-100 weight part, tackiness agent is the 1.5-25 weight part, described manganese source is Mn
3O
4And/or can access Mn after the roasting
3O
4The compound of manganese;
(2) mixture that step (1) is obtained carries out the first roasting;
(3) with the aqueous solution incipient impregnation of the product after step (2) roasting with the compound of silver, then kneading, moulding is respectively with Mn
3O
4And Ag
2The O meter, based on the manganese source of 100 weight parts, the aqueous solution of the compound of silver is the 8-35 weight part, the compound of described silver is can decompose after the roasting to obtain Ag
2The compound of the water miscible silver of O;
(4) product with step (3) moulding carries out burin-in process, then the solid after the burin-in process is carried out drying;
(5) the dried product of step (4) is carried out 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
4And described alkali metal hydroxide is decomposed obtain described alkalimetal oxide, 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 aforesaid method.
The third aspect the invention provides the application of a kind of aforesaid alkene reductor in the 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 the alkene deoxygenation conditions, alkene is carried out the gas phase deoxidation by the alkene reductor after reducing.
Alkene reductor of the present invention adopts the nano level TiO of modification by alkali metal
2Make carrier, the deoxidation capacity under the room temperature is high, and when preparation adopt a minute one-step baking, the manganese source is decomposed under comparatively high temps obtain Mn
3O
4, silver-colored compound is decomposed at a lower temperature obtains Ag
2O, avoided the Ag sintering, further improved the deoxidation capacity, the deoxidation capacity can reach 29.6ml/g, much larger than the deoxidation capacity that has now under the alkene reductor room temperature, therefore under identical deoxygenation conditions, also correspondingly be longer than the work-ing life of existing alkene reductor the work-ing life of alkene reductor of the present invention, and add tackiness agent, the mechanical resistance crushing strength is high, can reach 93 newton/cm; The deoxidation degree of depth has reduced by five times than prior art level less than 0.05ppm less than 0.01ppm; Reduction temperature is low, and is namely reducible under 150～160 ℃ of temperature, consistent with the reductor reduction temperature that existing polyolefin device can provide, 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 the room temperature, calculate according to the contriver, produce per year 300,000 tons of polyethylene devices room temperature not under the heating condition deoxidation can save units up to a million every year than 100 ℃ of lower deoxidations, saved the energy, reduced the discharging of greenhouse gases.Alkene reductor of the present invention can be widely used in industrial production.
Other features and advantages of the present invention will partly be described in detail in embodiment subsequently.
Embodiment
Below the specific embodiment of the present invention is elaborated.Should be understood that, embodiment described herein only is used 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) with the nano level TiO of manganese source and alkalimetal oxide and/or alkali metal hydroxide modification
2Mix with tackiness agent and to obtain mixture, respectively with Mn
3O
4, modification nano level TiO
2With the tackiness agent meter, based on the manganese source of 100 weight parts, the nano level TiO of modification
2Consumption be the 58-100 weight part, tackiness agent is the 1.5-25 weight part, described manganese source is Mn
3O
4And/or can access Mn after the roasting
3O
4The compound of manganese;
(2) mixture that step (1) is obtained carries out the first roasting;
(3) with the aqueous solution incipient impregnation of the product after step (2) roasting with the compound of silver, then kneading, moulding is respectively with Mn
3O
4And Ag
2The O meter, based on the manganese source of 100 weight parts, the aqueous solution of the compound of silver is the 8-35 weight part, the compound of described silver is can decompose after the roasting to obtain Ag
2The compound of the water miscible silver of O;
(4) product with step (3) moulding carries out burin-in process, then the solid after the burin-in process is carried out drying;
(5) the dried product of step (4) is carried out 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
4And described alkali metal hydroxide is decomposed obtain described alkalimetal oxide, the temperature of described the second roasting can make the compound decomposition of described silver obtain Ag
2O.
Room temperature among the present invention refers to 25 ℃.Ppm refers to volumetric concentration.
Nano level TiO
2Type Detitanium-ore-type, rutile-type and brookite type three types are arranged, preferably adopt nano level Detitanium-ore-type and/or nm-class rutile-type TiO
2Prepare the alkene reductor as support material, further the preferred nano level Detitanium-ore-type TiO that adopts
2Prepare the alkene reductor as support material.Nano level TiO among the present invention
2Refer to average particle size range does not reach the micron number magnitude in nanometer scale TiO
2, i.e. the TiO of median size below 1 μ m
2Non-nano level TiO
2Refer to average particle size range not in nanometer scale, the TiO more than nanometer scale
2
Median size among the present invention refers to volume average particle size, adopts transmission electron microscope to record.
According to the present invention, although adopt the nano level TiO of modification
2Carrier as the alkene reductor prepares the alkene reductor, and the nano level TiO of the consumption in manganese source, modification
2The consumption of consumption, tackiness agent and the concentration of the aqueous solution of the compound of silver and consumption so that with Mn
3O
4, modification nano level TiO
2, tackiness agent and Ag
2The O meter, based on the manganese source of 100 weight parts, the nano level TiO of modification
2Consumption be the 58-100 weight part, tackiness agent is the 1.5-25 weight part, the aqueous solution of compound of silver is the 8-35 weight part, can reach purpose of the present invention, but under the preferable case, the nano level TiO of modification
2Median size be 5-50nm, can further improve the deoxidation capacity under the alkene reductor room temperature that the inventive method makes, further prolong the work-ing life under the alkene reductor room temperature; Under the further preferable case, the nano level TiO of modification
2Median size be 5-20nm, can further improve the deoxidation capacity under the alkene reductor room temperature that the inventive method makes, further prolong the work-ing life under the alkene reductor room temperature.
The nano level TiO of modification
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 satisfying roasting
3O
4Get final product, can be the compound of the thinkable various manganese of those skilled in the art, be preferably selected from least a in the group that is 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 be selected from least a in the group that is formed by manganous carbonate, manganous oxalate, manganese acetate and formic acid manganese, more preferably manganous carbonate.
The median size in manganese source is preferably 20-70 μ m, can improve the mechanical resistance crushing strength of the alkene reductor that makes; 20-45 μ m more preferably can further improve the mechanical resistance crushing strength of the alkene reductor that makes.
Without particular requirement, as long as can reach purpose of the present invention, can by the thinkable various tackiness agents of those skilled in the art, be preferably cement and/or water glass for the tackiness agent among the present invention.In order further to improve the mechanical resistance crushing strength of the alkene reductor that makes, the median size of tackiness agent is preferably 20-70 μ m, more preferably 20-45 μ m.
Obtain the method for the required median size of manganese source and tackiness agent without particular requirement, can be the whole bag of tricks that this area is commonly used, the ball mill of for example manganese source and tackiness agent can being packed into grinds, and then equals to obtain after the sieve of required median size with the aperture.
The compound of silver is as long as obtain Ag for decomposing after the roasting
2The compound of the water miscible silver of O gets final product, and can by the compound of the thinkable various silver of those skilled in the art, be preferably Silver Nitrate.
The nano level TiO of modification
2Contain TiO
2And alkalimetal oxide and/or alkali metal hydroxide, in alkalimetal oxide, the nano level TiO of modification
2The quality percentage composition of middle alkalimetal oxide and/or alkali metal hydroxide is preferably 0.1-5%, 1-3% more preferably, TiO
2Content be preferably 95-99.9%, 97-99% more preferably.The nano level TiO of modification
2The quality percentage composition of middle alkalimetal oxide calculates according to feed ratio and gets.Alkalimetal oxide among the present invention is preferably one or more in sodium oxide, potassium oxide and the Lithium Oxide 98min, more preferably sodium oxide.The nano level TiO of modification
2In TiO
2Median size be 5-50nm, be preferably 5-20nm, specific surface area is 30-200m
2/ g is preferably 100-200m
2/ g, that those skilled in the art should understand that is the nano level TiO of modification
2The content of middle alkalimetal oxide seldom, modification is for TiO
2Particle diameter and the impact of specific surface area can ignore, can think TiO before and after the modification
2Particle diameter and specific surface area constant.
The consumption of preparation method's Raw of alkene reductor provided by the invention, i.e. the nano level TiO of manganese source and modification
2The consumption of consumption, tackiness agent and the concentration of the aqueous solution of the compound of silver and consumption so that respectively with Mn
3O
4, modification nano level TiO
2, tackiness agent and Ag
2The O meter, based on the manganese source of 100 weight parts, the nano level TiO of modification
2Be the 58-100 weight part, tackiness agent is the 1.5-25 weight part, and the aqueous solution of the compound of silver is the 8-35 weight part, is preferably the manganese source based on 100 weight parts, the nano level TiO of modification
2Consumption be the 58-85 weight part, tackiness agent is the 8-25 weight part, the aqueous solution of compound of silver is the 15-35 weight part, more preferably based on the manganese source of 100 weight parts, the nano level TiO of modification
2Be the 58-70 weight part, tackiness agent is the 15-25 weight part, and the aqueous solution of the compound of silver is the 20-35 weight part.
Nano level TiO for alkalimetal oxide and/or alkali metal hydroxide modification
2The preparation method without particular requirement, can be the whole bag of tricks that this area is commonly used, for example can be at nano level TiO
2Middle adding alkali metal hydroxide aqueous solution carries out incipient impregnation, then at 90-120 ℃ of lower dry 8-12h, namely gets the nano level TiO of alkali metal hydroxide modification
2If, dry rear at 250-450 ℃ of lower roasting 2-8h, namely get the nano level TiO of modification by alkali metal
2Because the nano level TiO of modification
2With carry out the first roasting after manganese source, tackiness agent mix, therefore, at the nano level TiO of preparation modification
2The time can not carry out first roasting, namely make first the nano level TiO of alkali metal hydroxide modification
2, until with carry out the first roasting, the nano level TiO of the first roasting post-modification after manganese source, tackiness agent mix
2Nano level TiO for modification by alkali metal
2The nano level TiO of preparation modification
2Maturing temperature be 250-450 ℃, the roasting of manganese source obtains Mn
3O
4Maturing temperature be 400-550 ℃, therefore the first roasting is preferably carried out under 400-450 ℃, further preferably at 400-450 ℃ of lower roasting 2-10h.
Nano level TiO with manganese source, modification
2Mix with tackiness agent and to obtain mixture, the method that mixes can adopt this area the whole bag of tricks commonly used without particular requirement, for example can be with the nano level TiO of manganese source, modification
2Putting into cone-type mixer with tackiness agent mixes.
With the aqueous solution incipient impregnation of the product after step (2) roasting with the compound of silver, then kneading, moulding is so that Mn
3O
4, modification nano level TiO
2, tackiness agent and silver the aqueous solution of compound even.For the shape after the method for incipient impregnation and kneading, moulding and kneading, the moulding without particular requirement, the aqueous solution that adds the compound of silver in for example can the product after step (2) roasting carries out incipient impregnation, then be prepared into the strip segment with banded extruder, also the product after step (2) roasting can be joined in the coater, the aqueous solution that sprays into the compound of silver carries out incipient impregnation, then is rolled onto sphere.
Among the present invention the product of step (3) moulding carried out burin-in process and be preferably the airtight placement of product with step (3) moulding, airtight being placed under the room temperature normal pressure gets final product, and the time of airtight placement is preferably 12-72h, more preferably 24-60h.Without particular requirement, can adopt the conventional the whole bag of tricks that adopts in this area to carry out drying for drying, dry condition optimization is at 80-150 ℃ of lower dry 5-12h, more preferably at 100-140 ℃ of lower dry 8-12h.
The second roasting is to obtain Ag for the compound decomposition that makes silver
2O, the condition optimization of roasting carries out under 200-300 ℃, more preferably at 200-300 ℃ of lower roasting 1-5h.
On the other hand, the invention provides a kind of alkene reductor by the aforesaid method preparation.The mean pore size of alkene reductor is preferably 10-50nm, and specific surface area is preferably 50-250m
2/ g.
Through XRD analysis, include stronger Mn by the alkene reductor of the inventive method preparation
3O
4Characteristic diffraction peak, TiO
2Characteristic peak and weak Ag
2The O characteristic peak.
Active constituent before the alkene reductor of the inventive method preparation uses in the reductor product is Ag
2O and Mn
3O
4, it should be appreciated by those skilled in the art that needs the scene that this active ingredient is reduced into active constituent Ag and the MnO with deoxidizing capacity when using.Equally, the alkene reductor after reducing is after after a while deoxidation is used, and the Ag of lower valency and MnO can be oxidized to the Ag of high valence state
2O and Mn
3O
4When oxygen level after alkene reductor complete deactivation or the deoxidation when requiring index, need again reducing/regenerating reductor, reductor of the present invention can on-the-spot reducing/regenerating, reuses.The active ingredient that has deoxy activity under the room temperature mainly is the Ag of high dispersing.
The concrete reductive condition of alkene reductor is preferably: logical temperature is 130-160 ℃ hydrogen or hydrogen and N
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 that 150～160 ℃ hydrogeneous volume fraction is hydrogen and the N of 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 the alkene deoxidation.Have no special requirements for concrete application, 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 the alkene deoxygenation conditions, alkene is carried out the gas phase deoxidation by the alkene reductor after reducing.
Have no special requirements for concrete alkene method of deoxidation, can adopt the conventional the whole bag of tricks that adopts in this area, the alkene that for example can will contain 2-5 carbon atom in fixed-bed reactor carries out the gas phase deoxidation by the alkene reductor through reduction, oxygen level is 1-100ppm in the alkene, and the alkene volume space velocity is 100-3000h
-1, the service temperature of fixed-bed reactor is 20-100 ℃, pressure is 0.1-10MPa.The alkene that more preferably will contain 2-4 carbon atom in fixed-bed reactor carries out the gas phase deoxidation by the alkene reductor through reduction, and oxygen level is 1-5ppm in the alkene, and the 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 preferred implementation of the present invention in detail; but the present invention is not limited to the detail in the above-mentioned embodiment, in technical conceive scope 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.
Need to prove in addition, each concrete technical characterictic described in above-mentioned embodiment in reconcilable situation, can make up by any suitable mode, for fear of unnecessary repetition, the present invention is to the no longer separately explanation of various possible array modes.
In addition, also can carry out arbitrary combination between the various embodiment of the present invention, 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 Examples, 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, under 150 ℃, pass into the hydrogen volume mark and be 1% nitrogen, at volume space velocity 200h
-1Stop to pass into behind the reduction 12h under the condition.After the cooling, at pressure 0.4MPa, under 25 ℃ of the temperature, pass into ethene, the volume of ethylene air speed is 1500h
-1, entrance oxygen level 1000ppm.After system brought into operation, the concentration of residual oxygen after the observation deoxidation in the ethene was found after the deoxidation concentration of residual oxygen in the ethene all the time less than 0.01ppm, when the concentration of residual oxygen in the ethene after the deoxidation stops experiment during greater than 0.01ppm.The present invention is defined as after the deoxidation concentration of residual oxygen (ppm) in the alkene with the deoxidation degree of depth under the alkene reductor room temperature; The oxygen volume that the deoxidation capacity definition is removed during less than 0.01ppm in the deoxidation degree of depth (under the standard state corresponding milliliter number), divided by the quality of reductor, measure unit is ml/g.
In following embodiment and Comparative Examples, alkene reductor mechanical resistance crushing strength adopts ZQJ-II intelligence intensity meter.Measure the side crushing strength that 50 length randomly drawing are cut into the reductor finished product of 5mm for strip-shaped deoxidizer, take arithmetical av as measurement result, the newton/cm of unit; To spherical reductor, measure the crushing strength of 50 the reductor finished product of randomly drawing, take arithmetical av as measurement result, the newton of unit/grain.
In following embodiment and Comparative Examples, 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.
Be that 9.8nm, specific surface area are 160m in the 650g median size
2The Detitanium-ore-type TiO of/g
2Middle adding aqueous sodium hydroxide solution carries out incipient impregnation, with Na
2The O meter, aqueous sodium hydroxide solution is 13g, then obtains the TiO of sodium hydroxide modification at 100 ℃ of lower dry 10h
2, the TiO of sodium hydroxide modification
2With median size be the MnCO of 35 μ m
3, and median size is that the cement mixing of 35 μ m is even, MnCO
3, the sodium hydroxide modification TiO
2With the consumption of cement so that respectively with Mn
3O
4, the sodium hydroxide modification TiO
2With the cement meter, based on the MnCO of 1000g
3, the TiO of sodium hydroxide modification
2Be 650g, cement is 200g, then will mix the mixture that obtains and carry out the first roasting 8h under 430 ℃, the nano level TiO of the modification after the roasting
2In, Na
2The quality percentage composition of O is 2%.
Add AgNO in the product after the first roasting
3Solution carries out incipient impregnation, AgNO
3The concentration of solution and consumption are so that with Mn
3O
4And Ag
2The O meter is based on the MnCO of 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 then at 120 ℃ of lower dry 8h, then carries out the second roasting 3h under 250 ℃, is prepared into the alkene reductor.The deoxidation capacity, the deoxidation degree of depth and the mechanical resistance crushing strength that record the alkene reductor that makes see Table 1.
Embodiment 2
This embodiment is used for illustrating the preparation method of alkene reductor provided by the invention.
Be that 5nm, specific surface area are 200m in the 580g median size
2The Detitanium-ore-type TiO of/g
2Middle adding aqueous sodium hydroxide solution carries out incipient impregnation, with Na
2The O meter, aqueous sodium hydroxide solution is 18g, then obtains the TiO of sodium hydroxide modification at 120 ℃ of lower dry 8h
2, the TiO of sodium hydroxide modification
2With median size be the MnCO of 20 μ m
3, and median size is that the cement mixing of 20 μ m is even, MnCO
3, the sodium hydroxide modification TiO
2With the consumption of cement so that respectively with Mn
3O
4, the sodium hydroxide modification TiO
2With the cement meter, based on the MnCO of 1000g
3, the TiO of sodium hydroxide modification
2Be 580g, cement is 150g, then will mix the mixture that obtains and carry out the first roasting 2h under 450 ℃, the nano level TiO of the modification after the roasting
2In, Na
2The quality percentage composition of O is 3%.
Product after the first roasting is joined in the coater, spray into AgNO
3Solution carries out incipient impregnation, AgNO
3The concentration of solution and consumption are so that with Mn
3O
4And Ag
2The O meter is based on the MnCO of 1000g
3, AgNO
3Solution is 350g, is rolled onto the sphere of Φ 3mm, and then airtight placement 60h then at 140 ℃ of lower dry 5h, then carries out the second roasting 1h under 300 ℃, is prepared into the alkene reductor.The deoxidation capacity, the deoxidation degree of depth and the mechanical resistance crushing strength that record the alkene reductor that makes see Table 1.
Embodiment 3
This embodiment is used for illustrating the preparation method of alkene reductor provided by the invention.
Be that 20nm, specific surface area are 100m in the 700g median size
2The Detitanium-ore-type TiO of/g
2Middle adding aqueous sodium hydroxide solution carries out incipient impregnation, with Na
2The O meter, aqueous sodium hydroxide solution is 7g, then obtains the TiO of sodium hydroxide modification at 90 ℃ of lower dry 12h
2, the TiO of sodium hydroxide modification
2With median size be the MnCO of 45 μ m
3, and median size is that the cement mixing of 45 μ m is even, MnCO
3, the sodium hydroxide modification TiO
2With the consumption of cement so that respectively with Mn
3O
4, the sodium hydroxide modification TiO
2With the cement meter, based on the MnCO of 1000g
3, the TiO of sodium hydroxide modification
2Be 700g, cement is 250g, then will mix the mixture that obtains and carry out the first roasting 10h under 400 ℃, the nano level TiO of the modification after the roasting
2In, Na
2The quality percentage composition of O is 1%.
Add AgNO in the product after the first roasting
3Solution carries out incipient impregnation, AgNO
3The concentration of solution and consumption are so that with Mn
3O
4And Ag
2The O meter is based on the MnCO of 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 then at 100 ℃ of lower dry 12h, then carries out the second roasting 5h under 200 ℃, is prepared into the alkene reductor.The deoxidation capacity, the deoxidation degree of depth and the mechanical resistance crushing strength that record the alkene reductor that makes see Table 1.
Embodiment 4
Method according to embodiment 1 prepares the alkene reductor, and different is Detitanium-ore-type TiO
2Median size be 40nm, the deoxidation capacity, the deoxidation degree of depth and the mechanical resistance crushing strength that record the alkene reductor that makes see Table 1.
Embodiment 5
Method according to embodiment 1 prepares the alkene reductor, and different is Detitanium-ore-type TiO
2Specific surface area be 40m
2/ g, the deoxidation capacity, the deoxidation degree of depth and the mechanical resistance crushing strength that record the alkene reductor that makes see Table 1.
Embodiment 6
Method according to embodiment 1 prepares the alkene reductor, and different is AgNO
3The concentration of solution and consumption are so that with Mn
3O
4And Ag
2The O meter is based on the MnCO of 1000g
3, AgNO
3Solution is 100g, and the deoxidation capacity, the deoxidation degree of depth and the mechanical resistance crushing strength that record the alkene reductor that makes see Table 1.
Embodiment 7
Method according to embodiment 1 prepares the alkene reductor, and different is, with Mn
3O
4, the sodium hydroxide modification TiO
2, cement and Ag
2The O meter, MnCO
3Consumption be 900g, the TiO of sodium hydroxide modification
2Consumption, consumption and the AgNO of cement
3Concentration and the consumption of solution are constant, and the deoxidation capacity, the deoxidation degree of depth and the mechanical resistance crushing strength that record the alkene reductor that makes see Table 1.
Embodiment 8
Method according to embodiment 1 prepares the alkene reductor, and different is TiO
2Be rutile TiO
2, median size is that 10nm, specific surface area are 165m
2/ g, the deoxidation capacity, the deoxidation degree of depth and the mechanical resistance crushing strength that record the alkene reductor that makes see Table 1.
Embodiment 9
Method according to embodiment 1 prepares the alkene reductor, and different is, with Mn
3O
4With the cement meter, based on the MnCO of 1000g
3, cement is 50g, the deoxidation capacity, the deoxidation degree of depth and the mechanical resistance crushing strength that record the alkene reductor that makes see Table 1.
Embodiment 10
Method according to embodiment 1 prepares the alkene reductor, and different is, the median size of cement is 70 μ m, and the deoxidation capacity, the deoxidation degree of depth and the mechanical resistance crushing strength that record the alkene reductor that makes see Table 1.
Embodiment 11
Method according to embodiment 1 prepares the alkene reductor, and different is MnCO
3Median size be 70 μ m, the deoxidation capacity, the deoxidation degree of depth and the mechanical resistance crushing strength that record the alkene reductor that makes see Table 1.
Embodiment 12
Method according to embodiment 1 prepares the alkene reductor, and different is, with Na
2The O meter, aqueous sodium hydroxide solution is 3g, the nano level TiO of the modification that obtains
2In, Na
2The quality percentage composition of O is 0.5%, and the deoxidation capacity, the deoxidation degree of depth and the mechanical resistance crushing strength that record the alkene reductor that makes see Table 1.
Embodiment 13
Method according to embodiment 1 prepares the alkene reductor, and different is, with Na
2The O meter, aqueous sodium hydroxide solution is 34g, the nano level TiO of the modification that obtains
2In, Na
2The quality percentage composition of O is 5%, and the deoxidation capacity, the deoxidation degree of depth and the mechanical resistance crushing strength that record the alkene reductor that makes see Table 1.
Comparative Examples 1
Method according to embodiment 1 prepares the alkene reductor, and different is TiO
2Be Detitanium-ore-type non-nano level TiO
2, median size is 2 μ m, specific surface area is 150m
2/ g, the deoxidation capacity, the deoxidation degree of depth and the mechanical resistance crushing strength that record the alkene reductor that makes see Table 1.
Comparative Examples 2
Method according to embodiment 1 prepares the alkene reductor, and different is to be that 20 μ m, specific surface area are 300m with median size
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, the deoxidation capacity, the deoxidation degree of depth and the mechanical resistance crushing strength that record the alkene reductor that makes see Table 1.
Comparative Examples 3
Method according to embodiment 1 prepares the alkene reductor, and different is, does not add tackiness agent during preparation alkene reductor, and the deoxidation capacity, the deoxidation degree of depth and the mechanical resistance crushing strength that record the alkene reductor that makes see Table 1.
Comparative Examples 4
Method according to embodiment 1 prepares the alkene reductor, and different is, not to TiO
2Carry out modification, the deoxidation capacity, the deoxidation degree of depth and the mechanical resistance crushing strength that record the alkene reductor that makes see Table 1.
Comparative Examples 5
Be that 9.8nm, specific surface area are 160m in the 650g median size
2The Detitanium-ore-type TiO of/g
2Middle adding aqueous sodium hydroxide solution carries out incipient impregnation, with Na
2The O meter, aqueous sodium hydroxide solution is 13g, and is dry rear at 350 ℃ of lower roasting 6h then at 100 ℃ of lower dry 10h, obtains the nano level TiO of modification
2, wherein, Na
2The quality percentage composition of O is 2%.
Be the MnCO of 35 μ m with median size
3, the nano level TiO of the modification that makes
2, and median size is that the cement mixing of 35 μ m is even.MnCO
3, modification nano level TiO
2With the consumption of cement so that respectively with Mn
3O
4, modification nano level TiO
2With the cement meter, based on the MnCO of 1000g
3, the nano level TiO of modification
2Be 650g, cement is 200g, adds AgNO in the blend composition after mixing
3Solution carries out incipient impregnation, AgNO
3The concentration of solution and consumption are so that with Mn
3O
4And Ag
2The O meter is based on the MnCO of 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 then at 120 ℃ of lower dry 8h, then at 480 ℃ of lower roasting 5h, is prepared into the alkene reductor.The deoxidation capacity, the deoxidation degree of depth and the mechanical resistance crushing strength that record the alkene reductor that makes see Table 1.
Table 1 embodiment and Comparative Examples experimental result
| Embodiment | Deoxidation capacity (ml/g) | The deoxidation degree of depth (ppm) | The mechanical resistance crushing strength |
| 1 | 27.5 | 0.007 | 85 |
| 2 | 29.6 | 0.006 | 93 |
| 3 | 24.2 | 0.008 | 93 |
| 4 | 23.8 | 0.007 | 85 |
| 5 | 22.6 | 0.009 | 84 |
| 6 | 21.5 | 0.008 | 83 |
| 7 | 25.9 | 0.008 | 86 |
| 8 | 22.9 | 0.009 | 87 |
| 9 | 28.4 | 0.007 | 65 |
| 10 | 27.3 | 0.008 | 74 |
| 11 | 26.7 | 0.006 | 76 |
| 12 | 25.3 | 0.008 | 86 |
| 13 | 26.5 | 0.009 | 87 |
| Comparative Examples 1 | 14.1 | 0.021 | 65 |
| Comparative Examples 2 | 10.2 | 0.032 | 67 |
| Comparative Examples 3 | 29.9 | 0.008 | 50 |
| Comparative Examples 4 | 24.8 | 0.007 | 85 |
| Comparative Examples 5 | 26.4 | 0.008 | 81 |
(annotate: the unit of the mechanical resistance crushing strength of embodiment 2 is newton/grain, and the unit of the mechanical resistance crushing strength of all the other embodiment and Comparative Examples is newton/cm)
Embodiment 1 and Comparative Examples 1 are compared and can find out, non-nano level TiO
2, the deoxidation capacity of the alkene reductor of making obviously reduces; Embodiment 1 and Comparative Examples 2 are compared and can find 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 Examples 3 are compared and can find out, do not add tackiness agent, the mechanical resistance crushing strength of the alkene reductor of making obviously reduces, the deoxidation capacity of reductor descends to some extent behind the adding tackiness agent, but the mechanical resistance crushing strength of reductor is its prerequisite with industrial application value, the mechanical resistance crushing strength requires relevant with the loadings of alkene reductor, and general requirement is greater than 50 newton; Embodiment 1 and Comparative Examples 4 are compared and can find out, to TiO
2Carry out the alkaline modification of alkalimetal oxide, can improve the deoxidation capacity of the alkene reductor of making; Embodiment 1 and Comparative Examples 5 are compared and can find out, with MnCO
3Under comparatively high temps, carry out the first Roasting Decomposition and become Mn
3O
4After again with AgNO
3Then the solution incipient impregnation carries out at a lower temperature the second roasting and makes AgNO
3Resolve into Ag
2The alkene reductor that O obtains is compared with MnCO
3With AgNO
3The deoxidation effect of the alkene reductor that roasting obtains under comparatively high temps together behind the solution incipient impregnation is good, and theoretical derivation may be because MnCO
3Resolve into Mn fully
3O
4Need to be in roasting more than 400 ℃, and be easy to be partially sintered at silver more than 400 ℃, thus silver-colored dispersity in the alkene reductor that makes is reduced and cause.
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 because 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 that makes
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 the alkene reductor; Embodiment 1 and embodiment 7 compare and can find out, Mn in the alkene reductor that makes
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
4Be the less important activeconstituents in the alkene reductor, theoretical derivation may be since high dispersing at TiO
2Ag on the carrier than MnO easier with raw material in micro amount of oxygen oxidizing reaction at room temperature occurs; Embodiment 1 and embodiment 8 compared to find out rutile TiO
2The alkene reductor that makes is not as Detitanium-ore-type TiO
2The deoxidation effect of the alkene reductor that makes is good; Embodiment 1 and embodiment 9 are compared and can find out, the content of tackiness agent is higher in the alkene reductor that makes, and the mechanical resistance crushing strength of the alkene reductor of making is higher; Embodiment 1 and embodiment 10 are compared and can find out, the median size of tackiness agent is less, and the mechanical resistance crushing strength of the alkene reductor of making is higher; Embodiment 1 and embodiment 11 are compared and can find out, the median size in manganese source is less, and the mechanical resistance crushing strength of the alkene reductor of making is higher; Embodiment 1 and embodiment 12 and embodiment 13 are compared respectively and can find out, the nano level TiO of modification by alkali metal
2The quality percentage composition of middle alkalimetal oxide is too high or too low all to be unfavorable for the deoxidation of the alkene reductor that makes.
Alkene reductor of the present invention adopts the nano level TiO of modification by alkali metal
2Make carrier, the deoxidation capacity under the room temperature is high, and when preparation adopt a minute one-step baking, the manganese source is decomposed under comparatively high temps obtain Mn
3O
4, silver-colored compound is decomposed at a lower temperature obtains Ag
2O, avoided the Ag sintering, further improved the deoxidation capacity, the deoxidation capacity can reach 29.6ml/g, much larger than the deoxidation capacity that has now under the alkene reductor room temperature, therefore under identical deoxygenation conditions, also correspondingly be longer than the work-ing life of existing alkene reductor the work-ing life of alkene reductor of the present invention, and add tackiness agent, the mechanical resistance crushing strength is high, can reach 93 newton/cm; The deoxidation degree of depth has reduced by five times than prior art level less than 0.05ppm less than 0.01ppm; Reduction temperature is low, and is namely reducible under 150～160 ℃ of temperature, consistent with the reductor reduction temperature that existing polyolefin device can provide, 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 the room temperature, has saved the energy, has reduced the discharging of greenhouse gases, can be widely used in industrial production.
Claims (18)
1. the preparation method of an alkene reductor said method comprising the steps of:
(1) with the nano level TiO of manganese source and alkalimetal oxide and/or alkali metal hydroxide modification
2Mix with tackiness agent and to obtain mixture, respectively with Mn
3O
4, modification nano level TiO
2With the tackiness agent meter, based on the manganese source of 100 weight parts, the nano level TiO of modification
2Consumption be the 58-100 weight part, tackiness agent is the 1.5-25 weight part, described manganese source is Mn
3O
4And/or can access Mn after the roasting
3O
4The compound of manganese;
(2) mixture that step (1) is obtained carries out the first roasting;
(3) with the aqueous solution incipient impregnation of the product after step (2) roasting with the compound of silver, then kneading, moulding is respectively with Mn
3O
4And Ag
2The O meter, based on the manganese source of 100 weight parts, the aqueous solution of the compound of silver is the 8-35 weight part, the compound of described silver is can decompose after the roasting to obtain Ag
2The compound of the water miscible silver of O;
(4) product with step (3) moulding carries out burin-in process, then the solid after the burin-in process is carried out drying;
(5) the dried product of step (4) is carried out 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
4And described alkali metal hydroxide is decomposed obtain described alkalimetal oxide, the temperature of described the second roasting can make the compound decomposition of described silver obtain Ag
2O.
2. method according to claim 1, wherein, the burin-in process in the described step (4) is carried out airtight placement for the product with step (3) moulding.
3. method according to claim 1 and 2, wherein, the temperature of described the first roasting is 400-450 ℃, the temperature of described the second roasting is 200-300 ℃.
4. the described method of any one according to claim 1-3, wherein, the nano level TiO of described modification
2Median size be 5-50nm, be preferably 5-20nm.
5. the described method of any one according to claim 1-4, wherein, the nano level TiO of described modification
2Specific surface area be 30-200m
2/ g is preferably 100-200m
2/ g.
6. the described method of any one according to claim 1-5, wherein, the nano level TiO of described modification
2Nano level Detitanium-ore-type TiO for modification
2
7. the described method of any one according to claim 1-6, wherein, the compound of described manganese is to be selected from least a in the group that is comprised of 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, be preferably and be selected from least a in the group that is formed by manganous carbonate, manganous oxalate, manganese acetate and formic acid manganese, more preferably manganous carbonate.
8. the described method of any one according to claim 1-7, wherein, the median size in described manganese source is 20-70 μ m, is preferably 20-45 μ m.
9. the described method of any one according to claim 1-8, wherein, described tackiness agent is cement and/or water glass.
10. the described method of any one according to claim 1-9, wherein, the median size of described tackiness agent is 20-70 μ m, is preferably 20-45 μ m.
11. the described method of any one according to claim 1-10, wherein, the compound of described silver is Silver Nitrate.
12. the described method of any one according to claim 1-11, wherein, the nano level TiO of described modification
2Contain TiO
2With alkalimetal oxide and/or alkali metal hydroxide, and in alkalimetal oxide, the nano level TiO of described modification
2The quality percentage composition of middle alkalimetal oxide and/or alkali metal hydroxide is 0.1-5%, is preferably 1-3%, TiO
2Content be 95-99.9%, be preferably 97-99%.
13. the described method of any one according to claim 1-12, wherein, described alkalimetal oxide is one or more in sodium oxide, potassium oxide and the Lithium Oxide 98min, and described alkali metal hydroxide is one or more in sodium hydroxide, potassium hydroxide and the lithium hydroxide.
14. an alkene reductor is characterized in that, described alkene reductor is made by the described method of any one among the claim 1-13.
15. alkene reductor according to claim 14, wherein, the mean pore size of described alkene reductor is 10-50nm.
16. according to claim 14 or 15 described alkene reductors, wherein, the specific surface area of described alkene reductor is 50-250m
2/ g.
17. one kind such as the application of the described alkene reductor of any one among the claim 14-16 in the alkene deoxidation.
18. alkene method of deoxidation, described method comprises with the reducing gas that contains hydrogen reduces to the described alkene reductor of any one among the claim 14-16, then under the alkene deoxygenation conditions, alkene is carried out the gas phase deoxidation by the alkene reductor after reducing.
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