CN106513037B - A kind of preparation method of anti-silicon, sulfur resistive type dehydrogenation catalyst - Google Patents
A kind of preparation method of anti-silicon, sulfur resistive type dehydrogenation catalyst Download PDFInfo
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- CN106513037B CN106513037B CN201610916323.4A CN201610916323A CN106513037B CN 106513037 B CN106513037 B CN 106513037B CN 201610916323 A CN201610916323 A CN 201610916323A CN 106513037 B CN106513037 B CN 106513037B
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
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Abstract
The invention discloses the preparation methods of a kind of anti-silicon, sulfur resistive type dehydrogenation catalyst, comprising the following steps: (1) polyethylene glycol PEG-600 and triethanolamine TEA is added as buffer in HF solution, forms compound HF solution；(2) molecular sieve powder is added in compound HF solution；(3) solution after addition molecular sieve is stirred in 40~60 DEG C of temperature, then filtering, deionized water washing, drying obtain powder；(4) HNO is added in powder obtained in last step3It in solution, is stirred at room temperature, then is filtered, deionized water washing, drying, the molecular sieve carrier material after obtaining modification；(5) using molecular sieve carrier material obtained in last step as catalyst carrier, using the nitrate solution of infusion process carried noble metal, palladium nitrate, platinum nitrate, rhodium nitrate are dissolved in deionized water and form maceration extract, the modified molecular sieve carrier of incipient impregnation, by drying, roasting after dipping, dehydrogenation catalyst is obtained after cooling.
Description
Technical field
The present invention relates to the preparation methods of a kind of anti-silicon, sulfur resistive type dehydrogenation catalyst, belong to gas purification catalyst technology
Field.
Background technique
In rubbish landfill gas decontamination process, need to fall wherein a small amount of oxygen removing, i.e. deoxidation treatment link.
A kind of effective processing method is catalytic deoxidation in deoxidation treatment, i.e., using the methane component contained in rubbish landfill gas, leads to
It crosses using catalyst, makes oxygen and methane that oxidation reaction occur, generate water and carbon dioxide, thus by oxygen content control to wanting
Seek limit value hereinafter, and to water and CO 2, separated in subsequent decarburization and dehydration link.This method
The advantages of be that processing system process is simple, be convenient for industrial applications.
The dehydrogenation catalyst industrially used at present is mainly using activated alumina as noble metal (Pd, Pt, Rh of carrier
Deng) type catalyst, due to leading to higher cost containing noble metal, as it is desirable that noble metal catalyst have in actual operation compared with
Long service life.However, due to also containing type siloxane component and hydrogen sulfide in rubbish landfill gas, practice have shown that these two types of
The presence of component can cause irreversible inactivation to catalyst.Deactivation mechanism is that catalyst works in catalytic oxidation process
Temperature is higher, and in 300~500 DEG C of ranges, type siloxane component will form silicon oxide deposition in catalyst in this temperature environment
Active site is covered on surface, and 2 S component will form sulfate equally can cover active site and cause catalyst inactivation.
Since the presence of these two types of components increases the deactivation rate of dehydrogenation catalyst, lead to catalyst change cycle time, increases
Catalyst operating cost in deoxidation treatment.
Summary of the invention
The purpose of the present invention is to provide the preparation method of a kind of anti-silicon, sulfur resistive type dehydrogenation catalyst, have preferable anti-silicon,
The dehydrogenation catalyst of sulfur resistance.
The present invention adopts the following technical scheme: the preparation method of a kind of anti-silicon, sulfur resistive type dehydrogenation catalyst comprising following
Step: (1) it in HF solution is added polyethylene glycol PEG-600 and triethanolamine TEA as buffer, forms compound HF solution；(2)
It selects ETS-10 or ETS-4 as molecular sieve powder raw material, molecular sieve powder is added in compound HF solution；It (3) will be last
Solution after molecular sieve is added in step stirs in 40~60 DEG C of temperature, then filters, after being washed with deionized, dries
To powder；(4) HNO is added in powder obtained in last step3It in solution, is stirred at room temperature, then is filtered, deionization
Water washing, the powder then dried are by structure and surface-property-modifying treated molecular sieve carrier material；(5) will
For molecular sieve carrier material obtained in last step as catalyst carrier, the nitrate using infusion process carried noble metal is molten
Palladium nitrate, platinum nitrate, rhodium nitrate are dissolved in deionized water and form maceration extract by liquid, and incipient impregnation is modified molecular sieve supported
Body obtains dehydrogenation catalyst by drying, roasting after dipping after cooling.
HF concentration is 10~25 wt. %, PEG-600 levels range in compound HF solution in HF solution in step (1)
In 1~5 wt.%, TEA levels range in 4~16 wt.%.
In step (2), titanium silicon ratio is 1:3.5~1:5 in selected ETS-10 or ETS-4 molecular sieve powder raw material.
In step (2), molecular sieve powder is added in compound HF solution by 8~15 wt.% weight contents.
Using oscillation stirring or magnetic agitation, mixing time is 12~36h, deionized water washing for stirring in step (3)
Three times, drying temperature is 105 DEG C, and drying time is 5~10h.
In step (3), the process stir, be filtered, washed, drying is repeated three times.
HNO in step (4)3The concentration of solution is 30~60%, and weight ratio is added 20~38% in powder, is shaken at room temperature
Stirring or magnetic agitation 6h are swung, the stirring in step (4) is using oscillation stirring or magnetic agitation, mixing time 6h, deionization
Water washing three times, drying temperature is 105 DEG C, and drying time is 5~10h.
In step (5), palladium nitrate, platinum nitrate, rhodium nitrate total mol concentration are 0.01~0.04mol/L, leaching in maceration extract
Pd, Pt, Rh ratio are 10:6:3 in stain liquid.
In step (5), drying temperature is 105 DEG C, and drying time is 5~10h, and maturing temperature is 500~650 DEG C, roasting
Time is 5~8h.
The beneficial effects of the present invention are: the present invention using the Titanium Sieve Molecular Sieve of high silicon content as catalyst carrier substrate,
Titanium Sieve Molecular Sieve is surface-treated using comprising the hydrogen fluoride solution including buffer, the lattice silicon atom in carrier is taken off
It removes, and increases the surface acidity of carrier, in this way when the silicon atom in siloxane molecule can fill up missing on catalyst surface
Lattice silicon, it is strong additionally, due to surface acidity so as to avoid the silica harmful substance for forming covering active site, it can press down significantly
Absorption of the sulfur dioxide that hydrogen sulfide processed generates in oxidation on catalyst surface, also just further suppresses to form sulfate
The probability of inactivation.Using the catalyst of the same bullion content compared with the existing technology of dehydrogenation catalyst prepared by the present invention,
In carrying out rubbish landfill gas deoxidation treatment, depending on siloxanes in feeding gas and concentration of hydrogen sulfide difference, it can express apparent anti-
Inactivate performance.Experiment show when in feeding gas siloxane concentrations in 2mg/m3, concentration of hydrogen sulfide is in 1000mg/m3When, the present invention
The working time for the dehydrogenation catalyst prepared can be improved 3.5 times or more.The present invention is applied not only at the deoxidation of rubbish landfill gas
Reason, it can also be used in the deoxidation treatment of the gases such as biogas, coal bed gas, pyrolysis gas, synthesis gas.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.
A kind of specific embodiment of the present invention is as follows: the preparation method of the anti-silicon of the present embodiment, sulfur resistive type dehydrogenation catalyst, packet
Include following steps: (1) compound concentration is the HF solution of 10~25 wt. %, and polyethylene glycol PEG-600 and three is added in HF solution
Ethanol amine TEA forms compound HF solution, PEG-600 levels range is 1~5 in compound HF solution as buffer
Wt.%, TEA levels range are in 4~16 wt.%；(2) select titanium silicon than ETS-10 the or ETS-4 conduct for 1:3.5~1:5
Molecular sieve powder is added in compound HF solution by molecular sieve powder raw material by 8~15 wt.% weight contents；(3) by last step
Solution after molecular sieve is added in rapid stirs in 40~60 DEG C of temperature, using oscillation stirring or 12~36h of magnetic agitation, then
Filtering, is washed with deionized three times, and 105 DEG C of 5~10h of drying obtain powder, and the process stir, be filtered, washed, drying repeats
Three times；(4) HNO that concentration is 30~60% is added in powder finally obtained in last step3In solution, weight is added in powder
Ratio is stirred at room temperature 20~38%, using oscillation stirring or magnetic agitation 6h, then is filtered, is washed with deionized
Three times, then 105 DEG C of 5~10h of drying, obtained powder is by structure and surface-property-modifying treated molecular sieve carrier
Material；(5) using molecular sieve carrier material obtained in last step as catalyst carrier, using infusion process carried noble metal
Palladium nitrate, platinum nitrate, rhodium nitrate are dissolved in deionized water and form maceration extract by nitrate solution, palladium nitrate, nitric acid in maceration extract
Platinum, rhodium nitrate total mol concentration are 0.01~0.04mol/L, and Pd, Pt, Rh ratio are 10:6:3 in maceration extract, and incipient impregnation changes
Property after molecular sieve carrier, 5~10h is dried after dipping at 105 DEG C, roasts at 500~650 DEG C, is obtained after cooling later
Dehydrogenation catalyst.
Core point in dehydrogenation catalyst preparation of the present invention is above-mentioned steps (1) ~ (4) content, and step (2) is to be directed to
Property selected suitable carrier material i.e. titanium silicon molecular sieve ETS-4-10 or ETS-4 and corresponding titanium silicon ratio, step (3) is benefit
Fall the silicon atom in Titanium Sieve Molecular Sieve with the removing of HF acid, step (1) ~ (4) are to embody have by catalyst carrier to be directed to
Property and it is innovative to sex work, it can be ensured that anti-silicon, the sulfur resistance of catalyst is made in step (5), step (5) is final
Obtain a steps necessary of catalyst.The present invention, as catalyst carrier substrate, is adopted using the Titanium Sieve Molecular Sieve of high silicon content
Titanium Sieve Molecular Sieve is surface-treated with comprising the hydrogen fluoride solution including buffer, the lattice silicon atom in carrier is taken off
It removes, and increases the surface acidity of carrier, in this way when the silicon atom in siloxane molecule can fill up missing on catalyst surface
Lattice silicon, it is strong additionally, due to surface acidity so as to avoid the silica harmful substance for forming covering active site, it can press down significantly
Absorption of the sulfur dioxide that hydrogen sulfide processed generates in oxidation on catalyst surface, also just further suppresses to form sulfate
The probability of inactivation.Using the catalyst of the same bullion content compared with the existing technology of dehydrogenation catalyst prepared by the present invention,
In carrying out rubbish landfill gas deoxidation treatment, depending on siloxanes in feeding gas and concentration of hydrogen sulfide difference, it can express apparent anti-
Inactivate performance.Experiment show when in feeding gas siloxane concentrations in 2mg/m3, concentration of hydrogen sulfide is in 1000mg/m3When, the present invention
The working time for the dehydrogenation catalyst prepared can be improved 3.5 times or more.The present invention is applied not only at the deoxidation of rubbish landfill gas
Reason, it can also be used in the deoxidation treatment of the gases such as biogas, coal bed gas, pyrolysis gas, synthesis gas.
Claims (9)
1. the preparation method of a kind of anti-silicon, sulfur resistive type dehydrogenation catalyst, which is characterized in that it is the following steps are included: (1) is molten in HF
Polyethylene glycol PEG-600 and triethanolamine TEA is added as buffer in liquid, forms compound HF solution；(2) select ETS-10 or
Molecular sieve powder is added in compound HF solution by ETS-4 as molecular sieve powder raw material；(3) it will be added and divide in last step
Solution after son sieve stirs in 40~60 DEG C of temperature, then filters, and after being washed with deionized, drying obtains powder；(4) will
HNO is added in powder obtained in last step3It in solution, is stirred at room temperature, then is filtered, deionized water washing, then
Drying obtained powder is by structure and surface-property-modifying treated molecular sieve carrier material；It (5) will be in last step
Obtained molecular sieve carrier material is as catalyst carrier, using the nitrate solution of infusion process carried noble metal, by palladium nitrate,
Platinum nitrate, rhodium nitrate, which are dissolved in deionized water, forms maceration extract, the modified molecular sieve carrier of incipient impregnation, after dipping by
Drying, roasting, obtain dehydrogenation catalyst after cooling.
2. the preparation method of anti-silicon according to claim 1, sulfur resistive type dehydrogenation catalyst, it is characterised in that: in step (1)
HF concentration is 10~25 wt. % in HF solution, and PEG-600 levels range is dense in 1~5 wt.%, TEA in compound HF solution
Content range is spent in 4~16 wt.%.
3. the preparation method of anti-silicon according to claim 1, sulfur resistive type dehydrogenation catalyst, it is characterised in that: step (2)
In, titanium silicon ratio is 1:3.5~1:5 in selected ETS-10 or ETS-4 molecular sieve powder raw material.
4. the preparation method of anti-silicon according to claim 1, sulfur resistive type dehydrogenation catalyst, it is characterised in that: step (2)
In, molecular sieve powder is added in compound HF solution by 8~15 wt.% weight contents.
5. the preparation method of anti-silicon according to claim 1, sulfur resistive type dehydrogenation catalyst, it is characterised in that: in step (3)
Stirring using oscillation stirring or magnetic agitation, mixing time be 12~36h, deionized water wash three times, drying temperature 105
DEG C, drying time is 5~10h.
6. the preparation method of anti-silicon according to claim 1, sulfur resistive type dehydrogenation catalyst, it is characterised in that: step (3)
In, the process stir, be filtered, washed, drying repeats three times.
7. the preparation method of anti-silicon according to claim 1, sulfur resistive type dehydrogenation catalyst, it is characterised in that: in step (4)
HNO3The concentration of solution is 30~60%, and weight ratio is added 20~38% in powder, vibrates stirring or magnetic agitation at room temperature
6h, deionized water are washed three times, and drying temperature is 105 DEG C, and drying time is 5~10h.
8. the preparation method of anti-silicon according to claim 1, sulfur resistive type dehydrogenation catalyst, it is characterised in that: step (5)
In, palladium nitrate, platinum nitrate, rhodium nitrate total mol concentration are 0.01~0.04mol/L, Pd, Pt, Rh ratio in maceration extract in maceration extract
For 10:6:3.
9. the preparation method of anti-silicon according to claim 1, sulfur resistive type dehydrogenation catalyst, it is characterised in that: step (5)
In, drying temperature is 105 DEG C, and drying time is 5~10h, and maturing temperature is 500~650 DEG C, and calcining time is 5~8h.
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