CN1031746C - Preparation of effective Mo-family deoxidiser - Google Patents

Preparation of effective Mo-family deoxidiser Download PDF

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CN1031746C
CN1031746C CN 93112631 CN93112631A CN1031746C CN 1031746 C CN1031746 C CN 1031746C CN 93112631 CN93112631 CN 93112631 CN 93112631 A CN93112631 A CN 93112631A CN 1031746 C CN1031746 C CN 1031746C
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deoxidier
carrier
deoxidation
preparation
activity component
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CN1090221A (en
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于遵宏
于建国
沈才大
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East China University of Science and Technology
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Abstract

The present invention discloses an effective molybdenum deoxidant, and a preparation method and an application thereof. An active component of the deoxidant is a composition composed of molybdenum, tungsten, zirconium, cerium, iron, cobalt, nickel, oxygen and sulfur, wherein the molybdenum content is preferably selected within the range of 30 to 65%(wt). The preparation method comprises four steps: preparing a homogeneous solution of the active component; preparing a loading carrier; reducing activation treatment; and compression mould forming. The deoxidant obtained by the preparation method can deeply deoxidize general nitrogen, general hydrogen, argon gas, alkane mixing gas and mixed gas containing sulfur and CO to 0.1 ppm.

Description

Effective Mo-family deoxidier and method for making thereof and application
The present invention relates to a kind of deoxidier and method for making thereof and application, particularly a kind of high efficiency deoxidiser and the method for making and application that can contain deoxidation the gaseous mixture of carbon monoxide from sulfur-bearing.
As everyone knows, along with industrial expansions such as electronics, metallurgy, chemical industry, oil, the quality of high-purity gas and the requirement of quantity are grown with each passing day.In order to produce high-purity gas.Developed cryogenic rectification method in succession in the industrialization at present, low-temperature adsorption film diffusive separation method and catalysis absorption method etc., wherein catalysis absorption method, owing to adopt the deoxidier deoxidation, having the equipment simple operations makes things convenient for treating capacity big, advantages such as the deoxidation degree of depth is good have obtained using widely in recent years.Special gas magazine third phase review paper in 1986 domestic some kinds of comparatively ripe deoxidiers, as,
(1) copper deoxidier is representative with 0603 type deoxidized cooper mainly, at temperature 180-240 ℃, and air speed 1000-3000h -1Condition under, can be with general hydrogen, general nitrogen deoxidation to 10ppm, i.e. the deoxidation degree of depth can reach 10ppm, deoxidizing capacity can reach 10ml.O 2/ g. deoxidier.
(2) silver-colored deoxidier is representative with 201 striving of type AgX type gas agent mainly, at temperature 80-100 ℃, and air speed≤10000h -1Condition under, can be with the mist deoxidation to 1ppm, promptly the deoxidation degree of depth of this deoxidier can reach 1ppm, deoxidizing capacity can reach 10ml.O 2/ g. deoxidier.
(3) palladium deoxidier, the kind of such deoxidier is more, wherein:
(a) 105 type catalyzing deoxidation agents, at normal temperature, air speed 2000-5000h -1Condition under, can be with general hydrogen, general nitrogen deoxidation to 3-5ppm, i.e. the deoxidation degree of depth can reach 3-5ppm.
(b) 195 type catalyzing deoxidation agents, at normal temperature, air speed≤30000h -1Condition under, can be with general nitrogen deoxidation to 1ppm, promptly the deoxidation degree of depth of this deoxidier can reach 1ppm.
(c) DG-palladium catalyst, in room temperature-350 ℃, air speed 5000h -1Condition under, can be with general nitrogen, general hydrogen deoxidation to 2ppm, promptly the deoxidation degree of depth of this deoxidier can reach 2ppm.
(4) the nickel deoxidier mainly contains Ni-Cr 2O 3System (is representative with 651 type catalyst) and Ni-Al 2O 3System's (is representative with BH type deoxidier), wherein:
651 type catalyst, in room temperature-100 ℃, air speed 5000-6000h -1Condition under, can be with general nitrogen deoxidation to 5ppm, promptly the deoxidation degree of depth of this catalyst can reach 5ppm.
BH type deoxidier, in room temperature-200 ℃, air speed 300-500h -1Condition under, can be with general hydrogen, general nitrogen and argon gas and the deoxidation of alkanes gaseous mixture to 5ppm, promptly the deoxidation degree of depth of deoxidier can reach 5ppm, deoxidizing capacity can reach 25ml.O 2/ g. deoxidier.
Therefore, present industrial deoxidier, its deoxidation degree of depth is all not ideal enough, can not satisfy the requirement (deoxidation is to 0.1ppm) of high-purity gas, and in addition, above-mentioned various deoxidiers run into and contain H 2S, COS sulfides, and when containing the gas of impurity such as CO, all very easy poisoning is so its scope of application has been subjected to very big restriction.For this reason, developed manganese deoxidier in recent years again, as 401 type catalyst, in room temperature, air speed 10000h -1Condition under, can have good deoxidation effect with the gas deoxidation to 0.1ppm.But this deoxidier is very unstable, in case be exposed in the air, then emits a large amount of heat, lost efficacy immediately, thus should not store and transport, only suitable now-making-now-using, thereby limited its suitability for industrialized production.In addition, manganese deoxidier also is not suitable for and contains H 2The deoxidation treatment of foreign gases such as S, COS, CO.
The objective of the invention is to overcome the above-mentioned shortcoming of existing deoxidier.Providing a kind of production is easy, deoxidation effect good, (the deoxidation degree of depth can reach 0.1ppm, and deoxidizing capacity can reach 100ml.O 2/ deoxidier).The effective Mo-family deoxidier of the suitability for industrialized production in a large number of the stable storage that impurity such as resisting sulfide and carbon monoxide is poisoned.
Design of the present invention is such:
The inventor finds that by a large amount of experiments the oxide of molybdenum and the sulfide of molybdenum under certain conditions, all have good deoxidizing capacity, and this provides possibility for opening up industrial molybdenum deoxidier.Its deoxidation mechanism is based on chemisorbed and catalytic reaction makes hydrogen-oxygen reaction generate water, and process is as follows:
The chemisorbed of oxygen:
Figure C9311263100041
Wherein: X-be oxygen or element sulphur, or their mixture,
a＝1，1.5，2，2.5。The chemisorbed of hydrogen:
(2) oxygen atom and hydrogen atom catalytic reaction generation water take place on the molybdenum element surface:
(3)
Above-mentioned reaction ties up to deoxidation in the gas of hydrogenation, as deoxidation under the condition of hydrogenation not, after then deoxidier reaches oxygen saturation, needs logical separately H 2Regeneration.Deoxidier can be recycled.
In order to improve the deoxygenation function of molybdenum deoxidier, in the molybdenum deoxidier, introduce tungsten compound, by the cooperative effect of tungsten compound, improve the deoxidizing capacity of molybdenum deoxidier, in the molybdenum deoxidier, introduce iron compound or chromium compound or nickel compound, or their mixture, can improve the activity of molybdenum deoxidier, the reaction temperature when reducing deoxidation is introduced zirconium compounds or cerium compound in the molybdenum deoxidier, or their mixture, can improve the stability of molybdenum deoxidier.
The present invention also is achieved in that
The said effective Mo-family deoxidier of the present invention system is made of carrier and deoxy activity component.Suitable deoxy activity component content is 20～40% (wt), and all the other are carrier.Said carrier can be γ-Al 2O 3, active carbon, or both mixtures.Said deoxy activity component is the composition of molybdenum, tungsten, zirconium, cerium, iron, cobalt, nickel, oxygen, sulphur various element formation, and available following general formula is represented:
MoX aWX bAX cRX dWherein:
Mo--be molybdenum element;
W--be W elements;
X--be oxygen or element sulphur, or their mixture;
A--be iron, cobalt, nickel element, or their mixture;
R--be zirconium, Ce elements, or their mixture,
a＝1.0，1.5，2.0，2.5；
b＝1.0，1.5，2.0，2.5，3.0；
c＝1.0，1.5；
d＝1.5，2.0。The ratio of components scope of deoxy activity component is:
Mo：75～10％(wt)，
W： 0～29％(wt)，
A： 0～6％(wt)，
R： 0～5％(wt)，
O:0～30% (wt) or/and
S： 0～45％(wt)，
Wherein: the amount of oxygen and sulphur must be by forming required metal oxide or/and metal sulfide is complementary, and form 100% system.
The preparation method of effective Mo-family deoxidier of the present invention mainly comprises: the homogeneous phase solution of preparation deoxy activity component, preparation load carriers, four steps of reduction activation processing and compression molding.Wherein:
The homogeneous phase solution of preparation deoxy activity component:
Take by weighing material (as taking by weighing ammonium molybdate, ammonium tungstate, cobalt nitrate or nickel nitrate or ferric nitrate or their mixture and zirconium hydroxide or cerous nitrate or their mixture) by the proportioning that chooses, be dissolved in the water into homogeneous phase solution, filtering and impurity removing, add PH=8～12 of ammoniacal liquor regulator solution, obtain solution (I);
The preparation of load carriers:
Under stirring condition, [ratio as carrier is 60～80% (wt)] according to a certain percentage, with granularity be the 80-100 sieve aperture/centimetre 2γ-Al 2O 3Or active carbon or their mixture, or, join in the solution (I) of adjusted good PH the saturated solution of aluminium colloidal sol or aluminum nitrate.When using γ-Al 2O 3Or active carbon or their mixtures when promptly using the immersion process for preparing load carriers, should flood more than 16 hours when making carrier; When aluminium colloidal sol or aluminum nitrate saturated solution were made carrier, the gained sediment was load carriers, and suitable slaking is more than 6 hours.With the load carriers of gained or sediment through filtering, after the washing, place drying box earlier, in 100 ℃～130 ℃ dry 8～12 hours down, roasting in muffle furnace then, sintering temperature is 350 ℃～550 ℃, and roasting time is 6～12 hours, obtains active less molybdenum system: compositions.
Reduction activation is handled:
Above-mentioned molybdenum system: compositions is placed reduction furnace, and reduction activation is 6～12 hours in the hydrogen of hydrogen or sulfur-bearing, and the reduction activation temperature is 200～500 ℃, obtains the molybdenum system: compositions deoxidier (can be used as product uses) of overactivity.
Compression molding:
With above-mentioned overactivity molybdenum system: compositions deoxidier, at 3T/cm 2Press under be molded into the commercially available standardization product commonly used-effective Mo-family deoxidier grain products of φ 5 * 3 or φ 5 * 5.
The effective Mo-family deoxidier that obtains according to above-mentioned prescription and preparation method is used for general nitrogen, general hydrogen, argon gas, alkanes gaseous mixture and sulfur-bearing, contains the deoxidation of the gaseous mixture of CO, and its deoxidation degree of depth all can reach 0.1～0.2ppm, and its effect is as shown in table 1.
Table 1 sequence number is handled the object working condition can reach the deoxidation degree of depth
Normal pressure, 150 ℃
Air speed 1000h -11 general hydrogen deoxidation H 2: 98%Mol 0.2ppm
N 2：1.5％Mol
O 2：0.5％Mol
Normal pressure, 165 ℃ of 2 general nitrogen deoxidation air speed 1000h -10.1ppm
N 2：99.5％Mol
O 2：0.5％Mol
Normal pressure, normal temperature
Air speed 1000h -1
H 2：40.2％Mol
Sulfur-bearing, contain CO mixing N 2: 29.4%Mol3 qi exhaustion oxygen, as water CO:25.0%Mol 0.1ppm
Coal gas deoxidation CO 2: 4.8%Mol
O 2：0.4％Mol
H 2S：0.11％Mol
Other: 0.09%Mol
Normal pressure, normal temperature
Air speed 1000h -14 argon gas deoxidation Ar:83.7%Mol 0.2ppm
N 2：16.0％Mol
O 2：0.3％Mol
Normal pressure, temperature 〉=150 ℃
Air speed 1000h -15 argon gas deoxidation Ar:83.7%Mol 0.1ppm
N 2：16.0％Mol
O 2：0.3％Mol
Normal pressure, temperature 〉=150 ℃ 6 air speed 10000h -1
General nitrogen deoxidation N 2: 99.5%Mol 0.1ppm
O 2：0.5％Mol
Normal pressure, normal temperature
Air speed 5000h -1
H 2：40.2％Mol
N 2：29.4％Mol
Sulfur-bearing, contain the CO gaseous mixture
CO:25.0%Mol7 deoxidation such as water-gas CO 2: 4.8%Mol
Deoxidation O 2: 0.4%Mol 0.1ppm
H 2S：0.11％Mol
Other: 0.09%Mol
Normal pressure, temperature≤150 ℃
H 2: the general hydrogen deoxidation of 98.0%Mol8 N 2: 1.5%Mol 0.1ppm
O 2：0.5％Mol
Continuous table sequence number is handled the object working condition and can be reached the deoxidation degree of depth
Pressure: 0.3～0.7MPa
Temperature: 185 ℃
Air speed: 10000h -19 general nitrogen deoxidation N 2: 99.5%Mol≤0.1ppm
O 2：0.5％Mol
Pressure: 0.3～0.4MPa
Temperature: 160 ℃
Air speed: 10000h -1
H 2: the general hydrogen deoxidation of 98%Mol10 N 2: 1.5%Mol≤0.2ppm
O 2：0.5％Mol
Pressure: 0.1～1.2MPa
Temperature: normal temperature
Air speed: 1000h -1
H 2：40.2％Mol
N 2：29.4％Mol
Sulfur-bearing, contain CO mixed C O:25.0%Mol11 qi exhaustion oxygen such as water-gas CO 2: 4.8%Mol
Deoxidation O 2: 0.4%Mol 0.1ppm
H 2S：0.11％Mol
Other: 0.09%Mol
Normal pressure, temperature 〉=150 ℃
Air speed 10000h -1
Methane: 40%Mol12 alkanes gaseous mixture ethane: 30%Mol
Deoxidation butane: 29.5%Mol 0.1ppm
O 2: 0.5%Mol by table 1 as seen:
The said effective Mo-family deoxidier of the present invention, its deoxidation degree of depth can reach 0.1ppm, not only
Be applicable to general hydrogen, general nitrogen, argon gas and the deoxidation of alkanes gaseous mixture, and be specially adapted to contain
Sulphur, contain the deoxidation of the gaseous mixture of CO, this is that prior art is incomparable.
In addition, the said effective Mo-family deoxidier of the present invention, the experiment proved that: its deoxidizing capacity can reach 100mlO 2/ g deoxidier is more than 4 times of prior art; Can reach more than half a year its service life (referring to that an activation processing is to the interval between another time activation processing), is existing more than 25 times of deoxidier life-span.Therefore, it has the wide industrial application prospect.
Further illustrate content of the present invention below in conjunction with embodiment, but these examples do not limit protection scope of the present invention.
Embodiment 1
With (NH 4) 5H 5[H 2(WO 4) 6] H 2O 14g, (NH 4) 4Mo 7O 246H 2O 20g and Zr (OH) 42g is dissolved in 200g H 2Among the O, filtering and impurity removing, the PH=8-12 of dropping ammonia regulator solution.Under agitation, adding contains 320 gram Al (NO 3) 3Saturated solution, generate gelatinous precipitate, slaking is after 6 hours, with this sedimentation and filtration, washing, earlier 115 ℃ dry 12 hours down, roasting in Muffle furnace then, sintering temperature is 350-550 ℃, roasting time is 6-12 hour.Containing H at last 2Reduction activation was handled 8 hours in the hydrogen of S, and reduction temperature is 400 ℃, promptly obtains the said effective Mo-family deoxidier of the present invention, and its ratio of components is:
Carrier: Al 2O 3, 70% (wt), deoxy activity component: 30% (wt);
The ratio of components of deoxy activity component is:
Mo：30.8％(wt)，
W： 27.3％(wt)，
Zr：3.3％(wt)，
O： 12.9％(wt)，
S： 25.7％(wt)。
On press, be molded into the commercially available prod again.
Embodiment 2
Except carrier with the active carbon, all the other conditions are all with embodiment 1, the addition of active carbon is 76.6g, dip time is 20 hours.Can obtain the said effective Mo-family deoxidier of the present invention equally, its ratio of components is:
Carrier: active carbon 70% (wt), deoxy activity component: 30% (wt);
The ratio of components of deoxy activity component is:
Mo：30.8％(wt)；
W： 27.3％(wt)；
Zr：3.3％(wt)；
O： 12.9％(wt)；
S： 25.7％(wt)。
On press, be molded into the commercially available prod again.
Embodiment 3
With Co (NO 3) 310g, (NH 4) 6Mo 7O 246H 2O 40g, Zr (OH) 42g, (NH 4) 5H 5[H 2(WO 4) 6] H 2O 10g is dissolved in 400g H 2Among the O, filtering and impurity removing, the pH value of dropping ammonia regulator solution are 8-12, add under strong agitation and contain 50.3g Al (OH) 3Aluminium colloidal sol, active carbon 32.9g, precipitation slaking 16 hours, behind the filtration washing, earlier 110-130 ℃ dry 10 hours down, then 300-550 ℃ of following roasting 6～12 hours, containing H again 2Reduction activation was handled 10 hours in the hydrogen of S, and reduction temperature is 300 ℃, promptly obtains the said effective Mo-family deoxidier of the present invention, and its ratio of components is:
Carrier: (Al 2O 3+ active carbon): 60% (wt),
Deoxy activity component: 40% (wt).
The ratio of components of deoxy activity component is:
Mo： 49.5％(wt)
W： 7.8％(wt)
Zr： 2.6％(wt)
Co： 5.5％(wt)
O： 11.5％(wt)
S： 23.0％(wt)
On press, be molded into the commercially available prod again.
Embodiment 4
Except the condition variation that reduction activation is handled, all the other conditions are all with embodiment 3.
The condition that reduction activation is handled is: handled 8 hours down in 500 ℃ in hydrogen, promptly obtain effective Mo-family deoxidier of the present invention, its ratio of components is:
Carrier (Al 2O 3+ active carbon): 62.9% (wt)
Deoxy activity component: 37.1% (wt)
The ratio of components of the deoxy activity component of deoxidier is:
Mo： 56％(wt)
W： 8.9％(wt)
Zr： 2.9％(wt
Co： 6.2％(wt)
O： 26％(wt)
Compression molding becomes the commercially available prod on press again, and the gained deoxidier should carry out deoxidation in adding nitrogen atmosphere, and the deoxidation degree of depth can reach 0.1ppm.
Embodiment 5
Except using Ce (NO 3) 36H 2O replaces Zr (OH) 4Outward, all the other conditions are all with embodiment 3.Ce (NO 3) 36H 2The O addition is 3.5g.Obtain effective Mo-family deoxidier of the present invention, its ratio of components is:
Carrier (Al 2O 3+ active carbon): 60% (wt), deoxy activity component: 40% (wt);
The ratio of components of deoxy activity component is:
Mo：49.8％(wt)， W： 7.9％(wt)，
Ce：2.6％(wt)，
Co：5.5％(wt)，
O： 11.4％(wt)，
S： 22.8％(wt)。
Be molded into the commercially available prod again on press, its deoxidation degree of depth can reach 0.1ppm.
Embodiment 6
With Co (NO 3) 310g, (NH 4) 6Mo 7O 246H 2O 40g, Ce (NO 3) 36H 2O 2g and (NH 4) 5H 5[H 2(WO 4) 6] H 2O 10g is dissolved in 400g H 2Among the O, filtering and impurity removing, the pH value of dropping ammonia regulator solution are 8-12, add under strong agitation and contain 111.5g Al (OH) 3Aluminium colloidal sol, precipitation slaking 10 hours is filtered, after the washing, 110-130 ℃ dry 10 hours down, then 500 ℃ of following roastings 8 hours, containing H again 2Handled 12 hours down in 500 ℃ in the hydrogen of S.Obtain the said effective Mo-family deoxidier of the present invention, its ratio of components is:
Carrier (Al 2O 3): 60% (wt),
Deoxy activity component: 40% (wt).
The ratio of components of deoxy activity component is:
Mo： 44.7％(wt)，
W： 7.1％(wt)，
Ce： 2.3％(wt)，
Co： 4.9％(wt)，
S： 41％(wt)。
Be molded into the commercially available prod at last on press, its deoxidation degree of depth can reach 0.1ppm.

Claims (5)

1. an effective Mo-family deoxidier is made of carrier and deoxy activity component, it is characterized in that:
(1) composition of said deoxy activity component for constituting by molybdenum, tungsten, zirconium, cerium, iron, cobalt, nickel, oxygen, sulphur various element, available following general formula is represented:
MoX a·WX b·AX c·RX d
Wherein:
Mo-molybdenum element;
W-W elements;
X-oxygen or element sulphur, or their mixture;
A-iron or cobalt or nickel element, or their mixture;
R-be zirconium or cerium, or their mixture;
A-can in 1.0,1.5,2.0,2.5, choose;
B-can in 1.0,1.5,2.0,2.5,3.0, choose;
C-can in 1.0,1.5, choose;
D-can in 1.5,2.0, choose.
(2) said carrier is Al 2O 3, active carbon, or their mixture.
(3) carrier with the ratio of deoxy activity component is:
Carrier: 80～60% (wt);
Deoxy activity component: 20～40% (wt).
2. deoxidier as claimed in claim 1 is characterized in that the ratio of components scope of deoxy activity component is:
Mo：75～10％(wt)； W：0～19％(wt)；
A：0～6％(wt)； R：0～5％(wt)；
O:0～30% (wt) and/or S:0～45% (wt).
Wherein: the amount of oxygen and sulphur must be by forming required metal oxide or/and metal sulfide is complementary,
And form 100% system.
3. deoxidier as claimed in claim 2 is characterized in that the molybdenum content in the deoxy activity component is chosen in 30～65% (wt) scope.
4. as the described deoxidier of one of claim 1～3, its preparation technology mainly comprises the homogeneous phase solution of preparing the deoxidier active component in proportion, preparation load carriers, and three steps of reduction activation processing, wherein:
Said preparation homogeneous phase solution also comprises pH=8～12 with the ammoniacal liquor regulator solution;
Said preparation carrier, except adding in proportion the carrier, when also comprising with the immersion process for preparing load carriers, should flood at least 16 hours, when preparing load carriers with aluminium colloidal sol or aluminum nitrate saturated solution, sediment slaking 6 hours at least, the load after will filtering then, washing, drying was 8～12 hours under 110～130 ℃, 350～550 ℃ of roastings 6～12 hours;
Said reduction activation is treated at hydrogen or is containing H sReduction was handled 6～12 hours in the hydrogen of S, and reduction temperature is 200～500 ℃.
5. as the described deoxidier of one of claim 1～3, can be applicable to general nitrogen, general hydrogen, argon gas, alkanes gaseous mixture and sulfur-bearing, contain the degree of depth deoxidation of the gaseous mixture of CO.
CN 93112631 1993-12-24 1993-12-24 Preparation of effective Mo-family deoxidiser Expired - Fee Related CN1031746C (en)

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Publication number Priority date Publication date Assignee Title
CN1332753C (en) * 2005-06-20 2007-08-22 天津化工研究设计院 Sulphur resisting catalyzing deoxidation agent and its production process
CN100402140C (en) * 2006-07-11 2008-07-16 湖北省化学研究院 Sulfur-proof deoxidizing agent and its preparing and use
CN104888798B (en) * 2015-06-10 2017-12-19 西南化工研究设计院有限公司 A kind of high activated catalyst for rich CO gas sulfur-tolerance deoxidation and preparation method thereof
CN107362661B (en) * 2017-09-14 2019-09-10 中南大学 A kind of gas cleaning plant and its application
CN113511951A (en) * 2020-04-10 2021-10-19 中国石油化工股份有限公司 Method for deoxidizing unsaturated hydrocarbon gas
CN112717685B (en) * 2020-12-18 2023-03-24 大连凯特利催化工程技术有限公司 Purifying agent for removing trace impurities in high-purity gas and preparation method and application thereof

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