CN109550477A - A kind of application of titanium silicon dead catalyst and titanium silicon adsorbent - Google Patents
A kind of application of titanium silicon dead catalyst and titanium silicon adsorbent Download PDFInfo
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- CN109550477A CN109550477A CN201910045277.9A CN201910045277A CN109550477A CN 109550477 A CN109550477 A CN 109550477A CN 201910045277 A CN201910045277 A CN 201910045277A CN 109550477 A CN109550477 A CN 109550477A
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Abstract
The present invention discloses a kind of application of titanium silicon dead catalyst, is used to prepare the titanium silicon adsorbent for VOCs absorption.The preparation method of titanium silicon adsorbent, comprising the following steps: (1), by titanium silicon dead catalyst with binder, pore creating material and suitable quantity of water mix, obtain mixed material；(2), by the mixed material extruded moulding of step (1), intermediate products are obtained；(3), by intermediate products drying, the roasting of step (2), titanium silicon adsorbent is obtained.The invention also discloses a kind of titanium silicon adsorbents.Titanium silicon dead catalyst is prepared into the titanium silicon adsorbent for being used for VOCs absorption by the present invention, absorption property and total silicon ZSM-5 molecular sieve to VOCs is close, it is a kind of effective VOCs adsorbent, and reduce the processing cost of titanium silicon dead catalyst, and environmental pollution resulting from, improve resource reutilization rate.
Description
Technical field
The invention belongs to fine chemistry industry catalyst fields, and in particular to a kind of application and the absorption of titanium silicon of titanium silicon dead catalyst
Agent.
Background technique
Titanium Sieve Molecular Sieve is a kind of novel molecular sieve of last century early eighties Taramasso et al. exploitation, is by mistake
It crosses metal element of titanium and is introduced into a kind of miscellaneous original with special catalytic oxidation activity formed in the framework of molecular sieve with MFI structure
Sub- molecular sieve.
TS-1 molecular sieve not only has suction-operated and the Studies On The Shape-selective Catalysis of molecular sieve, and has both the catalysis of titanium active sites
Oxidation is known as " green catalysis " environmentally friendly catalyst system with the catalytic oxidation system of hydrogen peroxide composition, due to
Catalyst activity is high, simple process and it is pollution-free the advantages that receive the extensive concern of domestic and international researcher.Currently, titanium silicon point
Son sieve has more excellent in the reactions such as alkene epoxidation, aldehyde ketone ammoxidation, oxidation of alkanes, arene hydroxylation and alcohol oxidation
Catalytic activity and selectivity of product.Wherein the reactions such as cyclohexanone oxamidinating, epoxidation of propylene and phenol hydroxylation are real
Existing industrial amplification production.
In these organic catalysis oxidation reactions, catalyst deactivation phenomenom can all occur after operation a period of time.Currently, urging
The reason of agent inactivates mainly since organic matter through catalytic oxidation generates some by-products, these by-products or it is some its
His impurity deposits in molecular sieve surface and micropore canals, and molecular sieve pore passage blocking, framework titania activated centre is caused to be converted into
Extra-framework titanium form or loss, skeleton structure collapsing etc., eventually lead to catalyst inactivation.
Currently, there is more document and patent to report the regeneration method of deactivated titanium silicon molecular sieve, for example,
Deactivated titanium silicon catalyst is roasted at high temperature or deactivated titanium silicon molecular sieve roast again after sufficiently washing using different solvents
It burns；Deactivated titanium silicon molecular sieve is mixed with reclaimed rubber there are also some patents, is regenerated by hydrothermal crystallizing method.But it urges
Agent is inactivated after using using using after regeneration, repeatedly repeatedly after " use-regeneration-use " circulation, catalysis
The framework titania activated centre of agent is gradually decreased gradually to collapse imperfect with skeleton structure, causes catalyst thoroughly to inactivate, becomes useless
Catalyst.So how to handle these dead catalyst or these waste catalyst recoveries recycling allowed to have emphatically actual production
Want meaning.
A kind of preparation of Fe2O3 doping Titanium Sieve Molecular Sieve Fe-TS-1 composite photo-catalyst is described in patent CN107754843
Method and application.By Titanium Sieve Molecular Sieve and FeSO4Solution mixing is vigorously stirred, and grinds to obtain Fe- by drying, calcining and activating
TS-1 composite photo-catalyst, the catalyst accelerate the rate of Fenton's reaction.
A kind of load nano SnO is disclosed in patent CN106391108A2The synthetic method and application of/TS-1, as light
Catalyst is applied in dye wastewater treatment, such as waste water containing A-2BF acid red.Base of the invention in fresh Titanium Sieve Molecular Sieve
On plinth, there is the SnO of absorption and photocatalysis performance using sol-gel method synthesis2/ TS-1 catalyst.
Patent CN101648143A describe modified Pd/TS-1 catalyst of a kind of transition metal element and preparation method thereof and
Using.Active component Pd and transition metal element M is introduced in carrier Titanium Sieve Molecular Sieve, which is used for hydrogen, oxygen under normal pressure
The reaction of producing hydrogen peroxide by direct synthesis.
It is multiple that a kind of diatomite with hierarchical porous structure/nano-scale TS-1 Ti-Si zeolite is disclosed in patent CN106268936A
Condensation material and preparation method thereof.Catalyst has excellent photocatalytic degradation capability to crystal violet organic pollutant.
Patent CN107930687A discloses the method for modifying of TS-1 a kind of and its prepares third in solvent-free catalysis lactate
Application in keto ester.After carrying out the secondary steam treatment of steam treatment-secondary crystallization-to the TS-1 of commercialization, obtain
Modified catalyst TS-1 may be implemented efficient catalytic hydrogen peroxide oxidation lactate in solvent-free system and prepare pyruvate.
The above patent mainly disclose Titanium Sieve Molecular Sieve in addition to hydrogen peroxide form green catalysis oxidation system other than other
Using, but these applications are to be modified on the basis of fresh Ti-Si catalyst or load active component, for anti-
The recycling and reusing of the titanium silicon dead catalyst of middle inactivation is answered to be not directed to.
Summary of the invention
The first purpose of this invention is to provide a kind of application of titanium silicon dead catalyst, to improve titanium silicon dead catalyst
Resource reutilization rate, reduces environmental pollution.
It is technical solution of the present invention below:
The application of titanium silicon dead catalyst is used to prepare the titanium silicon adsorbent for volatile organic matter (VOCs) absorption.
According to the present invention, it those skilled in the art and is readily appreciated that, the VOCs is that the volatility of this field routine has
Machine object, such as: the VOCs is preferably in toluene, acetone, benzene, dimethylbenzene, styrene, chloroform, trichloroethanes and formaldehyde
One kind, but be not limited to mentioned kind.
According to the present invention, the titanium silicon dead catalyst is the oxygen of alkene epoxidation, arene hydroxylation, phenol hydroxylation, alcohol
The catalyst inactivated after being used for multiple times in change, ketone ammoxidation, ketone oxamidinating and oxidation of alkanes reaction.
Preferably, during the titanium silicon dead catalyst is cyclohexanone oxamidinating, epoxidation of propylene, phenol hydroxylation react repeatedly
The catalyst inactivated after use.
According to the present invention, the preparation method of the titanium silicon adsorbent, comprising the following steps:
(1), titanium silicon dead catalyst is mixed with appropriate binder, pore creating material and suitable water, obtains mixed material；
(2), by the mixed material extruded moulding of step (1), intermediate products are obtained；
(3), by intermediate products drying, the roasting of step (2), titanium silicon adsorbent is obtained.
According to the present invention, the mass ratio of the titanium silicon dead catalyst butt and pore creating material is 1:0.005~0.05；Titanium silicon
The mass ratio of silica or aluminum oxide is 1:0.02~0.2 in dead catalyst butt and binder.
It should be noted that above-mentioned titanium silicon dead catalyst is that titanium silicon dead catalyst wet feed and titanium silicon dead catalyst roast sample
One or both of.
According to the present invention, the binder in the step (1) is silica solution or Aluminum sol.
Preferably, the titanium silicon dead catalyst in the step (1) is titanium silicon dead catalyst wet feed, titanium silicon dead catalyst wet feed
It is directly mixed with binder and pore creating material, without washing early period and calcination process.
According to the present invention, it those skilled in the art and being readily appreciated that, the pore creating material is the pore creating material of this field routine,
Such as: the pore creating material is preferably polyethylene glycol 2000, methoxy poly (ethylene glycol), methylcellulose, graphite and sucrose, poly- first
One or more of organic polymers such as base methacrylate, cyclodextrin.
According to the present invention, in the step (2), the extruded moulding step using banded extruder commonly used in the prior art into
Row extruded moulding.
According to the present invention, in the step (3), the maturing temperature is 500~700 DEG C, and calcining time is 1~10h.
Second object of the present invention is to provide a kind of recycling and reusing method of titanium silicon dead catalyst, is used to prepare use
In the titanium silicon adsorbent of VOCs absorption, comprising the following steps:
(1), titanium silicon dead catalyst is mixed with appropriate binder, pore creating material and suitable water, obtains mixed material；
(2), by the mixed material extruded moulding of step (1), intermediate products are obtained；
(3), by intermediate products drying, the roasting of step (2), titanium silicon adsorbent is obtained.
Third object of the present invention is to provide a kind of titanium silicon adsorbent, uses titanium silicon dead catalyst for raw material, described
The preparation method of titanium silicon adsorbent includes following preparation step:
(1), titanium silicon dead catalyst is mixed with appropriate binder, pore creating material and suitable water, obtains mixed material；
(2), by the mixed material extruded moulding of step (1), intermediate products are obtained；
(3), by intermediate products drying, the roasting of step (2), titanium silicon adsorbent is obtained.
Compared with prior art, the present invention has following advantageous effects:
(1), titanium silicon dead catalyst is prepared into the titanium silicon adsorbent for being used for VOCs absorption by the present invention, to the adsorptivity of VOCs
Can be close with total silicon ZSM-5 molecular sieve, it is a kind of effective VOCs adsorbent, and reduce being processed into for titanium silicon dead catalyst
Sheet and environmental pollution resulting from improve resource reutilization rate.
(2), titanium silicon dead catalyst wet feed without washing and roasting, directly with binder and pore creating material extruded moulding, titanium
The organic by-products contained in silicon dead catalyst wet feed a one-step baking after shaping, can further generate some mesoporous, increase
Specific surface area and Kong Rong improve the absorption property of product；And process flow is simplified, entire technique is more economical.
Detailed description of the invention
Fig. 1 is the XRD diagram of titanium silicon dead catalyst in cyclohexanone oxamidinating reaction.
In figure, A curve refers to the XRD diagram of titanium silicon dead catalyst, and B curve refers to the XRD diagram of fresh Ti-Si catalyst, abscissa table
Show 2 angles θ, ordinate indicates feature peak intensity.
Fig. 2 is the gas chromatogram of tail gas before adsorbing.
Fig. 3 is the gas chromatogram of the tail gas of acquisition after titanium silicon adsorbent absorption of the invention.
Specific embodiment
Below in conjunction with specific embodiment, the invention will be further described.It should be understood that following embodiment is merely to illustrate this
Invention is not for limiting the scope of the invention.
Titanium silicon dead catalyst refer to alkene epoxidation, arene hydroxylation, phenol hydroxylation, the oxidation of alcohol, ketone ammoxidation,
The catalyst inactivated after being used for multiple times in ketone oxamidinating and oxidation of alkanes reaction.Inactivation refers in above-mentioned reaction, converts
It is following that rate is reduced to industrial application to require.Particularly, in cyclohexanone oxamidinating reaction, inactivation refers to that yclohexanone conversion ratio is low
It is lower than 98% in 95%, selectivity.
In following example 1-7, titanium silicon dead catalyst wet feed is the titanium silicon catalysis inactivated in cyclohexanone oxamidinating reaction
Agent wet feed.The yclohexanone conversion ratio of titanium silicon dead catalyst is lower than 97.8% lower than 94.9%, selectivity.Weigh a certain amount of titanium silicon
Dead catalyst wet feed, after 120 DEG C are dried overnight, calculating titanium silicon dead catalyst wet feed moisture content is 30%.
The XRD diagram of titanium silicon dead catalyst, as shown in figure 1 shown in A curve, the XRD diagram of fresh Ti-Si catalyst, B is bent as shown in figure 1
Shown in line.As seen from Figure 1, the molecular sieve crystallinity of the titanium silicon dead catalyst of inactivation is relatively low, and skeleton structure is destroyed serious.
Embodiment 1 prepares titanium silicon adsorbent
The preparation method of titanium silicon adsorbent, including following preparation step:
(1), successively weigh 30% silica solution of 2.3g and 0.14g polyethylene glycol 2000 to be added to 10g titanium silicon dead catalyst wet
In material, suitable water is added, stirring, which is uniformly mixed it, obtains wet cake W1；
(2), by the wet cake W of step (1)1It is put into banded extruder and carries out extrusion, obtain the intermediate products L of strip1；
(3), by the intermediate products L of step (2)1Drying, 550 DEG C of roasting 3h obtain the titanium silicon adsorbent T of strip1。
In the present embodiment, the mass ratio of the titanium silicon dead catalyst butt and polyethylene glycol 2000 is 1:0.02；Titanium silicon
The mass ratio of silica is 1:0.1 in dead catalyst butt and binder.
Detect T1Specific surface area and Kong Rong, the results are shown in Table 1.
Embodiment 2 prepares titanium silicon adsorbent
The preparation method of titanium silicon adsorbent, including following preparation step:
(1), successively weigh 30% silica solution of 0.5g and 0.14g polyethylene glycol 2000 to be added to 10g titanium silicon dead catalyst wet
In material, suitable water is added, stirring, which is uniformly mixed it, obtains wet cake W2；
(2), by the wet cake W of step (1)2It is put into banded extruder and carries out extrusion, obtain the intermediate products L of strip2；
(3), by the intermediate products L of step (2)2Drying, 500 DEG C of roasting 3h obtain the titanium silicon adsorbent T of strip2。
In the present embodiment, the mass ratio of the titanium silicon dead catalyst butt and polyethylene glycol 2000 is 1:0.02；Titanium silicon
The mass ratio of silica is 1:0.02 in dead catalyst butt and binder.
Detect T2Specific surface area and Kong Rong, the results are shown in Table 1.
Embodiment 3 prepares titanium silicon adsorbent
The preparation method of titanium silicon adsorbent, including following preparation step:
(1), successively weigh 30% silica solution of 4.7g and 0.14g polyethylene glycol 2000 to be added to 10g titanium silicon dead catalyst wet
In material, suitable water is added, stirring, which is uniformly mixed it, obtains wet cake W3；
(2), by the wet cake W of step (1)3It is put into banded extruder and carries out extrusion, obtain the intermediate products L of strip3；
(3), by the intermediate products L of step (2)3Drying, 500 DEG C of roasting 10h obtain the titanium silicon adsorbent T of strip3。
In the present embodiment, the mass ratio of the titanium silicon dead catalyst butt and polyethylene glycol 2000 is 1:0.02；Titanium silicon
The mass ratio of silica is 1:0.2 in dead catalyst butt and binder.
Detect T3Specific surface area and Kong Rong, the results are shown in Table 1.
Embodiment 4 prepares titanium silicon adsorbent
The preparation method of titanium silicon adsorbent, including following preparation step:
(1), it successively weighs 30% silica solution of 2.3g and 0.035g polyethylene glycol 2000 is added to 10g titanium silicon dead catalyst
In wet feed, suitable water is added, stirring, which is uniformly mixed it, obtains wet cake W4；
(2), by the wet cake W of step (1)4It is put into banded extruder and carries out extrusion, obtain the intermediate products L of strip4；
(3), by the intermediate products L of step (2)4Drying, 700 DEG C of roasting 1h obtain the titanium silicon adsorbent T of strip4。
In the present embodiment, the mass ratio of the titanium silicon dead catalyst butt and polyethylene glycol 2000 is 1:0.005；Titanium silicon
The mass ratio of silica is 1:0.1 in dead catalyst butt and binder.
Detect T4Specific surface area and Kong Rong, the results are shown in Table 1.
Embodiment 5 prepares titanium silicon adsorbent
The preparation method of titanium silicon adsorbent, including following preparation step:
(1), it successively weighs 30% silica solution of 2.3g and 0.35g methoxy poly (ethylene glycol) is added to 10g titanium silicon dead catalyst
In wet feed, suitable water is added, stirring, which is uniformly mixed it, obtains wet cake W5；
(2), by the wet cake W of step (1)5It is put into banded extruder and carries out extrusion, obtain the intermediate products L of strip5；
(3), by the intermediate products L of step (2)5Drying, 550 DEG C of roasting 5h obtain the titanium silicon adsorbent T of strip5。
In the present embodiment, the mass ratio of the titanium silicon dead catalyst butt and methoxy poly (ethylene glycol) is 1:0.05；Titanium
The mass ratio of silica is 1:0.1 in silicon dead catalyst butt and binder.
Detect T5Specific surface area and Kong Rong, the results are shown in Table 1.
Embodiment 6 prepares titanium silicon adsorbent
The preparation method of titanium silicon adsorbent, including following preparation step:
(1), it successively weighs 30% silica solution of 2.3g and 0.35g methylcellulose is added to 10g titanium silicon dead catalyst wet feed
In, suitable water is added, stirring, which is uniformly mixed it, obtains wet cake W6；
(2), by the wet cake W of step (1)6It is put into banded extruder and carries out extrusion, obtain the intermediate products L of strip6；
(3), by the intermediate products L of step (2)6Drying, 650 DEG C of roasting 3h obtain the titanium silicon adsorbent T of strip6。
In the present embodiment, the mass ratio of the titanium silicon dead catalyst butt and methylcellulose is 1:0.05；Titanium silicon is useless
The mass ratio of silica is 1:0.1 in catalyst butt and binder.
Detect T6Specific surface area and Kong Rong, the results are shown in Table 1.
Embodiment 7 prepares titanium silicon adsorbent
The preparation method of titanium silicon adsorbent, including following preparation step:
(1), it successively weighs 22% Aluminum sol of 3.2g and 0.14g graphite is added in 10g titanium silicon dead catalyst wet feed, then
Suitable water is added, stirring, which is uniformly mixed it, obtains wet cake W7；
(2), by the wet cake W of step (1)7It is put into banded extruder and carries out extrusion, obtain the intermediate products L of strip7；
(3), by the intermediate products L of step (2)7Drying, 600 DEG C of roasting 3h obtain the titanium silicon adsorbent T of strip7。
In the present embodiment, the mass ratio of the titanium silicon dead catalyst butt and graphite is 1:0.02；Titanium silicon dead catalyst
The mass ratio of aluminium oxide is 1:0.1 in butt and binder.
Detect T7Specific surface area and Kong Rong, the results are shown in Table 1.
Embodiment 8 prepares titanium silicon adsorbent
In the present embodiment, titanium silicon dead catalyst wet feed is the Ti-Si catalyst wet feed inactivated in propylene ring oxidation reaction.
Titanium silicon dead catalyst wet feed is dried, roasts experiment, the moisture content for calculating wet feed is 32%.
Other preparation conditions are same as Example 1, obtain the titanium silicon adsorbent T of strip8.Detect T8Specific surface area and hole
Hold, the results are shown in Table 1.
Embodiment 9 prepares titanium silicon adsorbent
In the present embodiment, titanium silicon dead catalyst wet feed is the Ti-Si catalyst wet feed inactivated in phenol hydroxylation reaction.It is right
Titanium silicon dead catalyst wet feed is dried, roasts experiment, and the moisture content for calculating wet feed is 31%.
Other preparation conditions are same as Example 1, obtain the titanium silicon adsorbent T of strip9.Detect T9Specific surface area and hole
Hold, the results are shown in Table 1.
Embodiment 10 prepares titanium silicon adsorbent
In the present embodiment, other preparation conditions are same as Example 1, and difference is, the pore creating material is 0.105g graphite
With 0.035g polyethylene glycol 2000.Obtain the titanium silicon adsorbent T of strip10。
In the present embodiment, the mass ratio of titanium silicon dead catalyst butt and pore creating material is 1:0.02.
Detect T10Specific surface area and Kong Rong, the results are shown in Table 1.
It should be understood readily by those skilled in this art, pore creating material of the invention, can also be made using routine in the prior art
Hole agent substitution, such as: sucrose, polymethyl methacrylate or cyclodextrin.
Embodiment 11 prepares titanium silicon adsorbent
The Ti-Si catalyst wet feed inactivated in a certain amount of cyclohexanone oxamidinating reaction is taken to be washed, dried, and 600
DEG C roasting 5h, obtain titanium silicon dead catalyst roasting sample.Sample preparation titanium silicon adsorbent, step are roasted using titanium silicon dead catalyst
It is as follows:
(1), it successively weighs 30% silica solution of 2.3g and 0.14g graphite is added in 7g titanium silicon dead catalyst roasting sample,
Suitable water is added, stirring, which is uniformly mixed it, obtains wet cake W11；
(2), by the wet cake W of step (1)11It is put into banded extruder and carries out extrusion, obtain the intermediate products L of strip11；
(3), by the intermediate products L of step (2)11Drying, 550 DEG C of roasting 3h obtain the titanium silicon adsorbent T of strip11。
In this comparative example, the mass ratio of the titanium silicon dead catalyst roasting sample and graphite is 1:0.02；Titanium silicon
The mass ratio that dead catalyst roasts silica in sample and binder is 1:0.1.
Detect T11Specific surface area and Kong Rong, the results are shown in Table 1.
Comparative example 1 prepares total silicon ZSM-5 adsorbent
(1), it takes a certain amount of total silicon ZSM-5 molecular sieve in 600 DEG C of roasting 5h, obtains ZSM-5 molecular sieve roasting sample.According to
It is secondary to weigh 30% silica solution of 2.3g and 0.14g polyethylene glycol 2000 is added in 7g ZSM-5 molecular sieve roasting sample, it adds
Suitable water, stirring, which is uniformly mixed it, obtains wet cake W12；
(2), by the wet cake W of step (1)12It is put into banded extruder and carries out extrusion, obtain the intermediate products L of strip12；
(3), by step (2) intermediate products L12Drying, 550 DEG C of roasting 3h obtain the ZSM-5 adsorbent T of strip12。
Detect T12Specific surface area and Kong Rong, the results are shown in Table 1.
The absorption property detection of embodiment 13, titanium silicon adsorbent
Since toluene and acetone are volatile organic matters most conventional in the prior art, the present embodiment uses toluene and acetone
For, toluene and acetone adsorption test are carried out to the titanium silicon adsorbent of the following example preparation at identical conditions, with detection
The absorption property of the titanium silicon adsorbent prepared under the conditions of different disposal.Specific adsorption step are as follows:
(1), the crucible after taking high-temperature roasting, its initial mass of precise M0(being accurate to four decimals), in crucible
Weigh 10g or so titanium silicon adsorbent (its mass M of accurate recording1)。
(2), the beaker of dry 50ml is taken, the toluene or acetone for taking 1/2 volume is contained, then titanium silicon adsorbent will be housed
Crucible and fill the beaker of volatile organic matter while being placed in absorber, after the glass cover for covering absorber, take out true
Sky is placed for 24 hours in 25 DEG C of environment of room temperature to guarantee that environment is closed, then by absorber, takes out afterwards fill titanium silicon adsorbent for 24 hours
Crucible simultaneously claims its gross weight, is denoted as M2。
Adsorb percentage composition=[(M2-M0-M1)/M1] × 100%.
Titanium silicon adsorbent T1-T11And total silicon ZSM-5 adsorbent T12VOCs absorption result it is as shown in table 1.
1 titanium silicon adsorbent T of table1-T11And total silicon ZSM-5 adsorbent T12VOCs absorption result
As can be seen from the data in table 1: titanium silicon adsorbent prepared by embodiment 11 and comparative example 1 it was found that, titanium silicon
The dead catalyst wet feed titanium silicon adsorbent T that extruded moulding obtains again after washing, roasting11, specific surface area and Kong Rong are opposite
In T12It decreases, VOCs absorption property is also compared with T12Difference, but still can be used as titanium silicon adsorbent.
The titanium silicon adsorbent T of Examples 1 to 10 preparation1-T10With T12It compares, there is suitable, even greater specific surface area
And Kong Rong, and titanium silicon adsorbent T1-T10With T12It is suitable to the absorption property of toluene and acetone, even better.Illustrate system of the present invention
Standby titanium silicon adsorbent, it is suitable with total silicon ZSM-5 molecular sieve to the absorption property of VOCs, even better, it is a kind of effective
VOCs adsorbent, and the processing cost and environmental pollution resulting from of titanium silicon dead catalyst are significantly reduced, improve resource
Reuse ratio.
Titanium silicon dead catalyst wet feed is without washing and roasting, and directly with binder and pore creating material extruded moulding, titanium silicon is useless
The organic by-products contained in catalyst wet feed a one-step baking after shaping, can further generate some mesoporous, and table is compared in increase
Area and Kong Rong improve the absorption property of product；And process flow is simplified, entire technique is more economical.
The Dynamic Adsorption of embodiment 14, methanol to olefins reaction tail gas
In order to preferably verify titanium silicon adsorbent to the absorption property of VOCs, with laboratory methanol to olefins reaction tail gas mould
Quasi- industry VOCs exhaust gas, has carried out Dynamic Adsorption, wherein contain in exhaust gas methanol, dimethyl ether, methane, C2-C5 alkane and alkene,
C6-C11 alkane, alkene, aromatic hydrocarbons etc., the VOCs before being adsorbed by gas chromatography detection in tail gas, gas chromatogram such as Fig. 2 institute
Show.
Steps are as follows for specific adsorption test:
(1), strip titanium silicon adsorbent pulverizes and sieves: taking 20g titanium silicon adsorbent T5It is ground, re-sieving obtains
The titanium silicon adsorbent of 10-20 mesh；
(2), adsorbent loads: taking the titanium silicon adsorbent 6g of 10-20 mesh, is packed into the adsorption tube of caliber 12mm；
(3), adsorption process: laboratory methanol to olefins reaction tail gas is pressed into flow 40ml/min and flow is 760ml/
The nitrogen of min is mixed into mixed gas tank, mixes 150 DEG C of gas tank heat preservation, and reaction end gas and nitrogen are sufficiently mixed laggard in mixed gas tank
Enter adsorption tube, absorption ten minutes later, acquires the tail gas in adsorption tanks exit, in the tail gas by gas chromatography detection acquisition
VOCs, gas chromatogram are as shown in Figure 3.
The gas-chromatography graph discovery of comparison diagram 2 and Fig. 3: methanol to olefins reaction tail gas passes through titanium silicon adsorbent T5Absorption
Afterwards, most organic matters is adsorbed, and illustrates titanium silicon adsorbent T5With excellent VOCs absorption property.
Specific embodiments of the present invention are described in detail above, but it is only used as example, the present invention is not intended to limit
In particular embodiments described above.To those skilled in the art, it any equivalent modifications to the practical progress and replaces
In generation, is also all among scope of the invention.Therefore, without departing from the spirit and scope of the invention made by equal transformation and repair
Change, all should be contained within the scope of the invention.
Claims (10)
1. the application of titanium silicon dead catalyst, which is characterized in that be used to prepare the titanium silicon adsorbent for VOCs absorption.
2. the application of titanium silicon dead catalyst according to claim 1, which is characterized in that the titanium silicon dead catalyst is alkene
In epoxidation, arene hydroxylation, phenol hydroxylation, the oxidation of alcohol, ketone ammoxidation, ketone oxamidinating and oxidation of alkanes reaction repeatedly
The catalyst inactivated after use.
3. the application of titanium silicon dead catalyst according to claim 2, which is characterized in that the titanium silicon dead catalyst is hexamethylene
Ketone oxamidinating, epoxidation of propylene, be used for multiple times in phenol hydroxylation reaction after the catalyst that inactivates.
4. titanium silicon dead catalyst application according to any one of claim 1-3, which is characterized in that the titanium silicon adsorbent
Preparation method, comprising the following steps:
(1), titanium silicon dead catalyst is mixed with appropriate binder, pore creating material and suitable water, obtains mixed material；
(2), by the mixed material extruded moulding of step (1), intermediate products are obtained；
(3), by intermediate products drying, the roasting of step (2), titanium silicon adsorbent is obtained.
5. the application of titanium silicon dead catalyst according to claim 4, which is characterized in that in the step (1), the titanium silicon
The mass ratio of dead catalyst butt and pore creating material is 1:0.005~0.05；Dioxy in titanium silicon dead catalyst butt and binder
SiClx or the mass ratio of aluminum oxide are 1:0.02~0.2.
6. titanium silicon dead catalyst application according to claim 4, which is characterized in that the bonding in the step (1)
Agent is silica solution or Aluminum sol.
7. titanium silicon dead catalyst application according to claim 4, which is characterized in that the titanium silicon in the step (1), which gives up, urges
Agent is titanium silicon dead catalyst wet feed, and titanium silicon dead catalyst wet feed is directly mixed with binder and pore creating material, washed without early period
It washs and calcination process.
8. titanium silicon dead catalyst application according to claim 4, which is characterized in that the pore-creating in the step (1)
Agent is organic polymer, is selected from polyethylene glycol 2000, methoxy poly (ethylene glycol), methylcellulose, graphite and sucrose, poly- methyl
One or more of methacrylate or cyclodextrin.
9. the application of titanium silicon dead catalyst according to claim 4, which is characterized in that in the step (3), the roasting
Temperature is 500~700 DEG C, and calcining time is 1~10h.
10. a kind of titanium silicon adsorbent, which is characterized in that use titanium silicon dead catalyst for raw material, the preparation of the titanium silicon adsorbent
Method includes following preparation step:
(1), titanium silicon dead catalyst is mixed with appropriate binder, pore creating material and suitable water, obtains mixed material；
(2), by the mixed material extruded moulding of step (1), intermediate products are obtained；
(3), by intermediate products drying, the roasting of step (2), titanium silicon adsorbent is obtained.
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| CN111871366A (en) * | 2020-07-31 | 2020-11-03 | 宁夏博实科技有限公司 | Adsorbent based on titanium-silicon molecular sieve and preparation method and application thereof |
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