CN102850164B - 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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- CN102850164B CN102850164B CN201110184594.2A CN201110184594A CN102850164B CN 102850164 B CN102850164 B CN 102850164B CN 201110184594 A CN201110184594 A CN 201110184594A CN 102850164 B CN102850164 B CN 102850164B
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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 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.Wherein ethene 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, further remove micro amount of oxygen in ethene and 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 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 generation high oxide reaches the decontamination effect improving of 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 one and has been unworthy of hydrogen reductor, 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 such as ethene and propylene micro amount of oxygen, 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 DEG C～1650 DEG C 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, and in order to improve deoxygenation temperature the work-ing life that extends alkene reductor, 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 DEG C), 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
2make carrier, 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, adopt the nano level TiO of modification by alkali metal
2make carrier, can further improve the deoxidation capacity under 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) by the nano level TiO of manganese source and alkalimetal oxide and/or alkali metal hydroxide modification
2mix and obtain mixture with tackiness agent, respectively with Mn
3o
4, modification nano level TiO
2with tackiness agent meter, the manganese source based on 100 weight parts, the nano level TiO of modification
2consumption be 58-100 weight part, tackiness agent is 1.5-25 weight part, described manganese source is Mn
3o
4and/or can obtain 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
4and can make described alkali metal hydroxide decompose and 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 up of 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 uses the reducing gas that contains hydrogen to reduce 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 the nano level TiO of modification by alkali metal
2make carrier, the deoxidation capacity under room temperature is high, and when preparation adopt a point 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, avoid Ag sintering, further improve deoxidation capacity, deoxidation capacity can reach 29.6ml/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, and add tackiness agent, mechanical resistance crushing strength is high, can reach 93 newton/cm; 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 DEG C 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, calculate according to contriver, produce per year 300,000 tons of polyethylene devices room temperature not under heating condition deoxidation can save every year units up to a million than deoxidation at 100 DEG C, 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 are described in detail the embodiment part 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 the nano level TiO of manganese source and alkalimetal oxide and/or alkali metal hydroxide modification
2mix and obtain mixture with tackiness agent, respectively with Mn
3o
4, modification nano level TiO
2with tackiness agent meter, the manganese source based on 100 weight parts, the nano level TiO of modification
2consumption be 58-100 weight part, tackiness agent is 1.5-25 weight part, described manganese source is Mn
3o
4and/or can obtain 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
4and can make described alkali metal hydroxide decompose and obtain described alkalimetal oxide, 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 DEG C.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
2prepare alkene reductor as support material, further preferably adopt nano level Detitanium-ore-type TiO
2prepare alkene reductor as support material.Nano level TiO in the present invention
2refer to average particle size range does not reach micron number magnitude TiO in nanometer scale
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 the nano level TiO of modification
2prepare alkene reductor as the carrier of alkene reductor, and the nano level TiO of the consumption in manganese source, modification
2the consumption of consumption, tackiness agent and concentration and the consumption of the aqueous solution of the compound of silver make with Mn
3o
4, modification nano level TiO
2, tackiness agent and Ag
2o meter, the manganese source based on 100 weight parts, the nano level TiO of modification
2consumption be 58-100 weight part, tackiness agent is 1.5-25 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, 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 extend the work-ing life under alkene reductor room temperature; Under 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 extend the work-ing life under 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 obtain 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 of free manganous carbonate, manganous oxalate, manganese acetate and formic acid manganese composition, 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 making; More preferably 20-45 μ m, can further improve the mechanical resistance crushing strength of the alkene reductor making.
Without particular requirement, as long as can reach object 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 in the present invention.In order further to improve the mechanical resistance crushing strength of the alkene reductor making, the median size of tackiness agent is preferably 20-70 μ m, more preferably 20-45 μ m.
Obtaining the method for the required median size of manganese source and tackiness agent without particular requirement, can be the conventional the whole bag of tricks in this area, for example, can pack manganese source and tackiness agent into ball mill and grind, and then equals to obtain after the sieve of required median size with aperture.
The compound of silver is as long as 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 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%, more preferably 1-3%, TiO
2content be preferably 95-99.9%, more preferably 97-99%.The nano level TiO of modification
2the quality percentage composition of middle alkalimetal oxide calculates and obtains according to feed ratio.Alkalimetal oxide in the present invention is preferably one or more in sodium oxide, potassium oxide and 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 is little, and modification is for TiO
2particle diameter and the impact of specific surface area negligible, can think TiO before and after 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 concentration and the consumption of the aqueous solution of the compound of silver make respectively with Mn
3o
4, modification nano level TiO
2, tackiness agent and Ag
2o meter, the manganese source based on 100 weight parts, the nano level TiO of modification
2for 58-100 weight part, tackiness agent is 1.5-25 weight part, and the aqueous solution of the compound of silver is 8-35 weight part, is preferably the manganese source based on 100 weight parts, the nano level TiO of modification
2consumption be 58-85 weight part, tackiness agent is 8-25 weight part, the aqueous solution of compound of silver is 15-35 weight part, the more preferably manganese source based on 100 weight parts, the nano level TiO of modification
2for 58-70 weight part, tackiness agent is 15-25 weight part, and the aqueous solution of the compound of silver is 20-35 weight part.
For the nano level TiO of alkalimetal oxide and/or alkali metal hydroxide modification
2preparation method without particular requirement, can be the conventional the whole bag of tricks in this area, can be for example at nano level TiO
2in add alkali metal hydroxide aqueous solution to carry out incipient impregnation, then dry 8-12h at 90-120 DEG C, obtains the nano level TiO of alkali metal hydroxide modification
2if, dry after at 250-450 DEG C roasting 2-8h, obtain the nano level TiO of modification by alkali metal
2.Due to the nano level TiO of modification
2after mixing with manganese source, tackiness agent, carry out the first roasting, therefore, at the nano level TiO of preparation modification
2time can first not carry out roasting, first make the nano level TiO of alkali metal hydroxide modification
2, after mixing with manganese source, tackiness agent, carry out the first roasting, the nano level TiO of the first roasting post-modification
2for the nano level TiO of modification by alkali metal
2.The nano level TiO of preparation modification
2maturing temperature be 250-450 DEG C, the roasting of manganese source obtains Mn
3o
4maturing temperature be 400-550 DEG C, therefore the first roasting is preferably carried out at 400-450 DEG C, further preferred roasting 2-10h at 400-450 DEG C.
By the nano level TiO of manganese source, modification
2mix and obtain mixture with tackiness agent, the method mixing, without particular requirement, can adopt the conventional the whole bag of tricks in this area, for example can be by the nano level TiO of manganese source, modification
2putting into cone-type mixer with tackiness agent mixes.
By the aqueous solution incipient impregnation of the product after step (2) roasting and silver-colored compound, then mediate, moulding, 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, 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 be prepared into strip segment with banded extruder, 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 being carried out to burin-in process is 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.Without particular requirement, can adopt the conventional the whole bag of tricks adopting in this area to be dried for dry, dry condition optimization is dry 5-12h at 80-150 DEG C, more preferably dry 8-12h at 100-140 DEG C.
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 DEG C, more preferably roasting 1-5h at 200-300 DEG C.
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 uses in reductor product is Ag
2o and Mn
3o
4, it should be appreciated by those skilled in the art that while use and need scene that this active ingredient is reduced into active constituent Ag and the MnO with deoxidizing capacity.Equally, when the alkene reductor after reduction is after deoxidation is after a while used, the Ag of lower valency and MnO can be oxidized to the Ag of high valence state
2o and Mn
3o
4.In the time that after alkene reductor complete deactivation or deoxidation, oxygen level is greater than requirement index, 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 DEG C
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 DEG C 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.Having no special requirements for concrete application, can be the application mode of this area routine, does not repeat them here.
Fourth aspect, the invention provides a kind of alkene method of deoxidation, described method comprises uses the reducing gas that contains hydrogen to reduce to above-mentioned alkene reductor, then, under alkene deoxygenation conditions, alkene is carried out to 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 adopting in this area, for example can be in fixed-bed reactor by the alkene that contains 2-5 carbon atom by carrying out gas phase deoxidation through the alkene reductor of 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 DEG C, pressure is 0.1-10MPa.More preferably in fixed-bed reactor by the alkene that contains 2-4 carbon atom by through reduction alkene reductor carry out gas phase deoxidation, in alkene, oxygen level is 1-5ppm, alkene volume space velocity is 500-2000h
-1, the service temperature of fixed-bed reactor is 20-30 DEG C, pressure is 0.1-5MPa.Carry out more preferably ethene or the propylene of alkene of deoxidation.
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, also can carry out arbitrary combination between 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 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 DEG C, 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 DEG C 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, stops experiment in the time that the concentration of residual oxygen in ethene after deoxidation is greater than 0.01ppm.The deoxidation degree of depth under alkene reductor room temperature is defined as after deoxidation concentration of residual oxygen (ppm) in alkene by the present invention; The oxygen volume (the milliliter number of correspondence under standard state) that deoxidation capacity definition is removed in the time that the deoxidation degree of depth is less than 0.01ppm, divided by the quality of reductor, measure unit is ml/g.
In following embodiment and comparative example, alkene reductor mechanical resistance crushing strength adopts ZQJ-II intelligence intensity meter.Measure 50 length randomly drawing and be cut into the side crushing strength of the reductor finished product of 5mm for strip-shaped deoxidizer, taking arithmetical av as measurement result, the newton/cm of unit; To spherical reductor, measure the crushing strength of the reductor finished product of 50 of randomly drawing, taking arithmetical av as measurement result, unit newton/grain.
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.
Be that 9.8nm, specific surface area are 160m in 650g median size
2the Detitanium-ore-type TiO of/g
2in add aqueous sodium hydroxide solution to carry out incipient impregnation, with Na
2o meter, aqueous sodium hydroxide solution is 13g, then at 100 DEG C, dry 10h obtains the TiO of sodium hydroxide modification
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, sodium hydroxide modification TiO
2make respectively with Mn with the consumption of cement
3o
4, sodium hydroxide modification TiO
2with cement meter, based on the MnCO of 1000g
3, the TiO of sodium hydroxide modification
2for 650g, cement is 200g, then at 430 DEG C, carries out the first roasting 8h, the nano level TiO of the modification after roasting by mixing the mixture obtaining
2in, Na
2the quality percentage composition of O is 2%.
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, 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, then airtight placement 48h, and then dry 8h at 120 DEG C then carries out the second roasting 3h at 250 DEG C, is prepared into alkene reductor.Record deoxidation capacity, the deoxidation degree of depth and the mechanical resistance crushing strength of the alkene reductor making in 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 580g median size
2the Detitanium-ore-type TiO of/g
2in add aqueous sodium hydroxide solution to carry out incipient impregnation, with Na
2o meter, aqueous sodium hydroxide solution is 18g, then at 120 DEG C, dry 8h obtains the TiO of sodium hydroxide modification
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, sodium hydroxide modification TiO
2make respectively with Mn with the consumption of cement
3o
4, sodium hydroxide modification TiO
2with cement meter, based on the MnCO of 1000g
3, the TiO of sodium hydroxide modification
2for 580g, cement is 150g, then at 450 DEG C, carries out the first roasting 2h, the nano level TiO of the modification after roasting by mixing the mixture obtaining
2in, Na
2the quality percentage composition of O is 3%.
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, based on the MnCO of 1000g
3, AgNO
3solution is 350g, is rolled onto the spherical of Φ 3mm, then airtight placement 60h, and then dry 5h at 140 DEG C then carries out the second roasting 1h at 300 DEG C, is prepared into alkene reductor.Record deoxidation capacity, the deoxidation degree of depth and the mechanical resistance crushing strength of the alkene reductor making in 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 700g median size
2the Detitanium-ore-type TiO of/g
2in add aqueous sodium hydroxide solution to carry out incipient impregnation, with Na
2o meter, aqueous sodium hydroxide solution is 7g, then at 90 DEG C, dry 12h obtains the TiO of sodium hydroxide modification
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, sodium hydroxide modification TiO
2make respectively with Mn with the consumption of cement
3o
4, sodium hydroxide modification TiO
2with cement meter, based on the MnCO of 1000g
3, the TiO of sodium hydroxide modification
2for 700g, cement is 250g, then at 400 DEG C, carries out the first roasting 10h, the nano level TiO of the modification after roasting by mixing the mixture obtaining
2in, Na
2the quality percentage composition of O is 1%.
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, 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, then airtight placement 24h, and then dry 12h at 100 DEG C then carries out the second roasting 5h at 200 DEG C, is prepared into alkene reductor.Record deoxidation capacity, the deoxidation degree of depth and the mechanical resistance crushing strength of the alkene reductor making in table 1.
Embodiment 4
Prepare alkene reductor according to the method for embodiment 1, different, Detitanium-ore-type TiO
2median size be 40nm, record deoxidation capacity, the deoxidation degree of depth and the mechanical resistance crushing strength of the alkene reductor making in table 1.
Embodiment 5
Prepare alkene reductor according to the method for embodiment 1, different, Detitanium-ore-type TiO
2specific surface area be 40m
2/ g, records deoxidation capacity, the deoxidation degree of depth and the mechanical resistance crushing strength of the alkene reductor making in table 1.
Embodiment 6
Prepare alkene reductor according to the method for embodiment 1, different, AgNO
3concentration and the consumption of solution make with Mn
3o
4and Ag
2o meter, based on the MnCO of 1000g
3, AgNO
3solution is 100g, records deoxidation capacity, the deoxidation degree of depth and the mechanical resistance crushing strength of the alkene reductor making in table 1.
Embodiment 7
Prepare alkene reductor according to the method for embodiment 1, different, with Mn
3o
4, sodium hydroxide modification TiO
2, cement and Ag
2o 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, record deoxidation capacity, the deoxidation degree of depth and the mechanical resistance crushing strength of the alkene reductor making in table 1.
Embodiment 8
Prepare alkene reductor according to the method for embodiment 1, different, TiO
2for rutile TiO
2, median size is that 10nm, specific surface area are 165m
2/ g, records deoxidation capacity, the deoxidation degree of depth and the mechanical resistance crushing strength of the alkene reductor making in table 1.
Embodiment 9
Prepare alkene reductor according to the method for embodiment 1, different, with Mn
3o
4with cement meter, based on the MnCO of 1000g
3, cement is 50g, records deoxidation capacity, the deoxidation degree of depth and the mechanical resistance crushing strength of the alkene reductor making in table 1.
Embodiment 10
Prepare alkene reductor according to the method for embodiment 1, different, the median size of cement is 70 μ m, records deoxidation capacity, the deoxidation degree of depth and the mechanical resistance crushing strength of the alkene reductor making in table 1.
Embodiment 11
Prepare alkene reductor according to the method for embodiment 1, different, MnCO
3median size be 70 μ m, record deoxidation capacity, the deoxidation degree of depth and the mechanical resistance crushing strength of the alkene reductor making in table 1.
Embodiment 12
Prepare alkene reductor according to the method for embodiment 1, different, with Na
2o meter, aqueous sodium hydroxide solution is 3g, the nano level TiO of the modification obtaining
2in, Na
2the quality percentage composition of O is 0.5%, records deoxidation capacity, the deoxidation degree of depth and the mechanical resistance crushing strength of the alkene reductor making in table 1.
Embodiment 13
Prepare alkene reductor according to the method for embodiment 1, different, with Na
2o meter, aqueous sodium hydroxide solution is 34g, the nano level TiO of the modification obtaining
2in, Na
2the quality percentage composition of O is 5%, records deoxidation capacity, the deoxidation degree of depth and the mechanical resistance crushing strength of the alkene reductor making in table 1.
Comparative example 1
Prepare alkene reductor according to the method for embodiment 1, 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 deoxidation capacity, the deoxidation degree of depth and the mechanical resistance crushing strength of the alkene reductor making in table 1.
Comparative example 2
Prepare alkene reductor according to the method for embodiment 1, different, be that 20 μ m, specific surface area are 300m by 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, record deoxidation capacity, the deoxidation degree of depth and the mechanical resistance crushing strength of the alkene reductor making in table 1.
Comparative example 3
Prepare alkene reductor according to the method for embodiment 1, different, while preparing alkene reductor, do not add tackiness agent, record deoxidation capacity, the deoxidation degree of depth and the mechanical resistance crushing strength of the alkene reductor making in table 1.
Comparative example 4
Prepare alkene reductor according to the method for embodiment 1, different, not to TiO
2carry out modification, record deoxidation capacity, the deoxidation degree of depth and the mechanical resistance crushing strength of the alkene reductor making in table 1.
Comparative example 5
Be that 9.8nm, specific surface area are 160m in 650g median size
2the Detitanium-ore-type TiO of/g
2in add aqueous sodium hydroxide solution to carry out incipient impregnation, with Na
2o meter, aqueous sodium hydroxide solution is 13g, then dry 10h at 100 DEG C, dry after at 350 DEG C roasting 6h, obtain the nano level TiO of modification
2, wherein, Na
2the quality percentage composition of O is 2%.
Be the MnCO of 35 μ m by median size
3, the nano level TiO of the modification making
2, and median size is that the cement mixing of 35 μ m is even.MnCO
3, modification nano level TiO
2make respectively with Mn with the consumption of cement
3o
4, modification nano level TiO
2with cement meter, based on the MnCO of 1000g
3, the nano level TiO of modification
2for 650g, cement is 200g, in the blend composition after mixing, adds AgNO
3solution carries out incipient impregnation, AgNO
3concentration and the consumption of solution make with Mn
3o
4and Ag
2o meter, 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, then airtight placement 48h, and then dry 8h at 120 DEG C, then roasting 5h at 480 DEG C, is prepared into alkene reductor.Record deoxidation capacity, the deoxidation degree of depth and the mechanical resistance crushing strength of the alkene reductor making in table 1.
Table 1 embodiment and comparative example experimental result
| Embodiment | Deoxidation capacity (ml/g) | The deoxidation degree of depth (ppm) | 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 example 1 | 14.1 | 0.021 | 65 |
| Comparative example 2 | 10.2 | 0.032 | 67 |
| Comparative example 3 | 29.9 | 0.008 | 50 |
| Comparative example 4 | 24.8 | 0.007 | 85 |
| Comparative example 5 | 26.4 | 0.008 | 81 |
(unit of the mechanical resistance crushing strength of note: embodiment 2 is newton/grain, and the unit of the mechanical resistance crushing strength of all the other embodiment and comparative example is newton/cm)
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, do not add tackiness agent, the mechanical resistance crushing strength of the alkene reductor of making obviously reduces, add the deoxidation capacity of reductor after tackiness agent to decline to some extent, but the mechanical resistance crushing strength of reductor is its prerequisite with industrial application value, mechanical resistance crushing strength requires relevant with the loadings of alkene reductor, and general requirement is greater than 50 newton; Embodiment 1 and comparative example 4 are compared and can be found 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 example 5 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 roasting more than 400 DEG C, and silver is easy to be partially sintered more than 400 DEG C, thus 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 the TiO little due to median size
2can be with the band-gap energy between conduction band 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; Embodiment 1 and embodiment 9 are compared and can be found out, in the alkene reductor making, the content of tackiness agent is higher, and the mechanical resistance crushing strength of the alkene reductor of making is higher; Embodiment 1 and embodiment 10 are compared and can be found 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 be found 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 be found out, the nano level TiO of modification by alkali metal
2the too high or too low deoxidation that is all unfavorable for the alkene reductor making of quality percentage composition of middle alkalimetal oxide.
Alkene reductor of the present invention adopts the nano level TiO of modification by alkali metal
2make carrier, the deoxidation capacity under room temperature is high, and when preparation adopt a point 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, avoid Ag sintering, further improve deoxidation capacity, deoxidation capacity can reach 29.6ml/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, and add tackiness agent, mechanical resistance crushing strength is high, can reach 93 newton/cm; 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 DEG C 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 (22)
1. a preparation method for alkene reductor, said method comprising the steps of:
(1) by the nano level TiO of manganese source and alkalimetal oxide and/or alkali metal hydroxide modification
2mix and obtain mixture with tackiness agent, respectively with Mn
3o
4, modification nano level TiO
2with tackiness agent meter, the manganese source based on 100 weight parts, the nano level TiO of modification
2consumption be 58-100 weight part, tackiness agent is 1.5-25 weight part, described manganese source is Mn
3o
4and/or can obtain 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
4and can make described alkali metal hydroxide decompose and obtain described alkalimetal oxide, 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, the nano level TiO of described modification
2median size be 5-50nm, the nano level TiO of described modification
2specific surface area be 30-200m
2/ g.
2. method according to claim 1, wherein, the temperature of described the first roasting is 400-450 DEG C, the temperature of described the second roasting is 200-300 DEG C.
3. method according to claim 1, wherein, the nano level TiO of described modification
2median size be 5-20nm.
4. method according to claim 1, wherein, the nano level TiO of described modification
2specific surface area be 100-200m
2/ g.
5. method according to claim 1, wherein, the nano level TiO of described modification
2for the nano level Detitanium-ore-type TiO of modification
2.
6. method according to claim 1, wherein, the compound of described manganese is at least one that select in the group of 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 composition.
7. method according to claim 6, wherein, the compound of described manganese is at least one that select in the group of free manganous carbonate, manganous oxalate, manganese acetate and formic acid manganese composition.
8. method according to claim 7, wherein, the compound of described manganese is manganous carbonate.
9. method according to claim 1, wherein, the median size in described manganese source is 20-70 μ m.
10. method according to claim 9, wherein, the median size in described manganese source is 20-45 μ m.
11. methods according to claim 1, wherein, described tackiness agent is cement and/or water glass.
12. methods according to claim 1, wherein, the median size of described tackiness agent is 20-70 μ m.
13. methods according to claim 10, wherein, the median size of described tackiness agent is 20-45 μ m.
14. methods according to claim 1, wherein, the compound of described silver is Silver Nitrate.
15. methods according to claim 1, 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%, TiO
2content be 95-99.9%.
16. methods according to claim 15, wherein, in alkalimetal oxide, the nano level TiO of described modification
2the quality percentage composition of middle alkalimetal oxide and/or alkali metal hydroxide is 1-3%, TiO
2content be 97-99%.
17. methods according to claim 1, wherein, described alkalimetal oxide is one or more in sodium oxide, potassium oxide and Lithium Oxide 98min, described alkali metal hydroxide is one or more in sodium hydroxide, potassium hydroxide and lithium hydroxide.
18. 1 kinds of alkene reductors, is characterized in that, described alkene reductor is made up of the method described in any one in claim 1-17.
19. alkene reductors according to claim 18, wherein, the mean pore size of described alkene reductor is 10-50nm.
20. alkene reductors according to claim 18, wherein, the specific surface area of described alkene reductor is 50-250m
2/ g.
The application in alkene deoxidation of 21. 1 kinds of alkene reductors as described in any one in claim 18-20.
22. 1 kinds of alkene method of deoxidations, described method comprises uses the reducing gas that contains hydrogen to reduce to the alkene reductor described in any one in claim 18-20, then under alkene deoxygenation conditions, alkene is carried out to gas phase deoxidation by the alkene reductor after reducing.
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