CN104646054B - Load solid acid catalyst, its preparation method and its application of Loprazolam - Google Patents
Load solid acid catalyst, its preparation method and its application of Loprazolam Download PDFInfo
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- CN104646054B CN104646054B CN201310585101.5A CN201310585101A CN104646054B CN 104646054 B CN104646054 B CN 104646054B CN 201310585101 A CN201310585101 A CN 201310585101A CN 104646054 B CN104646054 B CN 104646054B
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- catalyst
- solid acid
- highly
- olefin component
- acid catalyst
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The present invention relates to solid acid catalyst, its preparation method and its application of load Loprazolam, particularly, a kind of highly acid solid acid catalyst for olefin component in Arene removal is provided, wherein, the highly acid solid acid catalyst is in amorphous state, and includes Loprazolam amorphous silica and load thereon；The highly acid solid acid catalyst is made in the following manner：(1) in anhydrous conditions, tetraethyl orthosilicate is mixed（TEOS）And anhydrous formic acid, form uniform solution；(2) Loprazolam is added, continues to mix, forms catalyst intermediate；(3) catalyst intermediate is calcined, highly acid solid acid catalyst is formed.The present invention also provides the preparation method and applications of the highly acid solid acid catalyst.In the present invention, the catalyst shows good catalytic performance.The successful preparation and application of the catalyst open a new route for novel green industrialization.
Description
Technical field
The present invention relates to polyester synthesis industry, and in particular to one kind is used for alkene in Arene removal, especially paraxylene
The highly acid solid acid catalyst of component.The highly acid solid acid catalyst is with tetraethyl orthosilicate（TEOS）For silicon source, no water beetle
Acid is hydrolyst, and Loprazolam is sour modifying agent, is made in anhydrous conditions.The invention further relates to the highly acid solid
The preparation method of acid catalyst and the highly acid solid acid catalyst are used to go in the production of aromatic hydrocarbons, especially paraxylene
Except the application of olefin component.
Technical background
In recent years, with China's polyester industrial develop rapidly and private enterprise intervention energetically, China is to benzene two
The demand of formic acid constantly increases.Paraxylene is as the raw material immediately upstream of terephthalic acid (TPA), and whisk broom is not new yet for its demand
Record, is required for from external a large amount of imports every year.To meet the domestic market constantly expanded, economic development, country's examination ＆ approval are driven
A collection of paraxylene project.Because the olefin component in aromatic hydrocarbons material can have a strong impact on production in the production process of paraxylene
The progress of product purity and subsequent technique, so wherein having a step to be related to reduces the bromine index of aromatic hydrocarbons material.
The method of reduction bromine index has two kinds in general current art：
(1) hydrogenation technique, this technique is largely effective to reduction bromine index, but the technological operation requires that high, difficulty is big,
Due to using hydrogen its degree of danger also than larger, so using being limited in scope；
(2) clay-filtered technique, this technological operation very simple, safety coefficient is higher, is that most of refineries are used, but
That carclazyte in the technique is easily inactivated in the case of high bromine index, this resulted in a large amount of solid waste discharge and
The waste of national mineral resources.
To concentrate the strong point of above two technique, its deficiency is abandoned, people have studied many methods, for example, carclazyte is carried out
Various modifications, extend its service life, but its effect is still limited.
It is found that the pure methane sulfonic acid of liquid is for catalyzing aromatic hydrocarbon and the alkylated reaction of alkene in research before
With good effect, and Loprazolam is a kind of environment-friendly class organic acid, be can be analyzed within 28 days in natural environment
Carbon dioxide, water and sulfur dioxide, but it is considerably restricted using scope as liquid acid, it is difficult in existing process
Commercial scale is carried out to use.
At present, some some reports that sulfonic acid group is incorporated into silica surface are had, otherwise but their needs
Using template, otherwise the precursor of oxidant or sulfonic acid group is needed, and also the later stage needs to be washed, and this causes production
The environmental pollution of process, and operating process is cumbersome, is unfavorable for actual use.
In order to overcome above-mentioned many technical problems present in prior art, thus be badly in need of it is a kind of it is simple to operate, beneficial to reality
Border application, highly acid solid acid catalyst that is environment-friendly and can efficiently removing olefin component in aromatic hydrocarbons material.
The content of the invention
Therefore, one aspect of the present invention provides a kind of highly acid solid acid catalyst for olefin component in Arene removal,
Wherein, the highly acid solid acid catalyst is in amorphous state, and includes methane amorphous silica and load thereon
Sulfonic acid；The highly acid solid acid catalyst is made in the following manner：
(1) in anhydrous conditions, by tetraethyl orthosilicate（TEOS）With anhydrous formic acid mixing, uniform solution is formed；
(2) Loprazolam is added, continues to mix, forms catalyst intermediate；With
(3) catalyst intermediate is calcined, highly acid solid acid catalyst is formed.
In one embodiment of the present invention, the highly acid solid acid catalyst keeps original nothing after being calcined through 500 DEG C
Amorphous condition.
In one embodiment of the present invention, the specific surface area of the highly acid solid acid catalyst is 300-1000m2/
G, pore-size distribution is in 0.81-2.17nm.
On the other hand, the present invention, which is also provided, is used for the highly acid solid acid of olefin component in Arene removal described in a kind of prepare
The method of catalyst, methods described includes：
(1) in anhydrous conditions, tetraethyl orthosilicate is mixed（TEOS）And anhydrous formic acid, form uniform mixed solution；
(2) Loprazolam is added, continues to mix, forms catalyst intermediate；With
(3) catalyst intermediate is calcined, highly acid solid acid catalyst is formed.
In one embodiment of the present invention, the tetraethyl orthosilicate（TEOS）It is 1 with anhydrous formic acid mol ratio：0.05-
5。
In one embodiment of the present invention, in terms of the dry mass of amorphous silica, the amount of the Loprazolam is 1
Quality %-30 mass %.
In one embodiment of the present invention, it is small that the catalyst intermediate stands 1-6 at 20-100 DEG C, preferably 30 DEG C
When.
In one embodiment of the present invention, the catalyst intermediate is roasted at a temperature of 60-500 DEG C in Muffle furnace
Burn 1-6 hours.
In one embodiment of the present invention, tetraethyl orthosilicate is mixed（TEOS）It is by stirring 30-100 with anhydrous formic acid
What minute was carried out.
In a preferred embodiment, the stirring intensity for continuing mixing after Loprazolam is added higher than mixing tetraethyl orthosilicate
（TEOS）With the stirring intensity of anhydrous formic acid, continue to mix 1-100 minutes it is furthermore preferred that adding after Loprazolam.
The highly acid solid acid catalyst for being used for olefin component in Arene removal is provided in another aspect of the present invention to exist
It is used for the application for removing olefin component in the production of aromatic hydrocarbons, especially paraxylene.
Specifically (but not limited to), of the invention with tetraethyl orthosilicate（TEOS）For silicon source, anhydrous formic acid is urged for hydrolysis
Agent, Loprazolam is sour modifying agent, in anhydrous conditions, is prepared for highly acid solid acid catalyst.The highly acid solid
Acid catalyst shows prominent catalytic performance in olefin component in removing high bromine index aromatic hydrocarbons material, is the green of chemical enterprise
Color production opens a new route.
In a particular embodiment, the method for preparing highly acid solid acid catalyst is as follows：
(1) tetraethyl orthosilicate and anhydrous formic acid are added according to a certain percentage in stirred tank, preferred molar ratio is 1:0.05-
5, and stir 30-100 minutes, obtain uniform mixed solution；
(2) Loprazolam and then according to the 1%-30% of amorphous silica dry mass is added, stirring intensity is increased, continues
Stirring 1-100 minutes；
(3) obtained catalyst intermediate is stood 1-6 hours at 30 DEG C, be then transferred in Muffle furnace, in 60-
It is calcined 1-6 hours at a temperature of 500 DEG C, obtains highly acid solid acid catalyst catalyst.
In the present invention, the experiment for evaluating olefin component in Arene removal material is carried out in micro fixed-bed reactor.
Catalytic reaction condition is as follows：
2 grams of catalyst and 4 grams of quartz sands are fitted into reactor according to the order of quartz sand-catalyst-quartz sand, in temperature
60-300 DEG C of degree, pressure 1.0-2.5MPa, weight space velocity 1-30h-1Under conditions of, react 8 hours.Sampling analysis per hour,
Sample bromine index is analyzed with bromine valency bromine index instrument.
In the present invention, evaluating catalyst method is visible《For the acid for the modification clay that Trace Olefins are removed from aromatic hydrocarbons
Property and catalytic performance and its industrial test (Acidic and Catalytic Properties of Modified Clay for
Removing Trace Olefin from Aromatics and Its Industrial Test)》；Xin Pu,Nai-
Wang Liu, Zheng-hong Jiang, and Li Shi.；" the Chemical Engineering and industrial research of American Chemical Society
（Ind.Eng.Chem.Res.）" volume 2012,51, the 13891-13896 pages.
In the present invention, the bromine index analysis process is referred in chemical industry standard HG/T2825-2009 at the beginning of deolefination
The determination step for the activity that begins.
Moreover, the specific metering system of " the N2 adsorption-desorptions isothermal curve " of the present invention is according to national standard GB/T19587-
2004 are carried out.
The specific metering system of the pore size distribution curve of the present invention is carried out according to national standard GB/T19587-2004.
The specific metering system of the XRD of the present invention is carried out according to national standard GB/T19421.1-2003.
Highly acid solid acid catalyst prepared by the present invention has the characteristic of obvious amorphous silica.Through XRD points
It can be seen that the preceding structure compared of catalyst and load after load Loprazolam does not substantially change after analysis.In addition, the highly acid
The heat resistance of solid acid catalyst is obviously improved, and original amorphous state is still maintained through 500 DEG C of calcined catalysts.Compare table
Areal analysis result is shown：The specific surface area of highly acid solid acid catalyst of the present invention is in 300-1000m2Between/g, aperture point
Cloth is in 0.81-2.17nm.
Brief description of the drawings
Fig. 1 is the highly acid solid acid catalyst sample of the load Loprazolam prepared in the present invention according to embodiment 1
Nitrogen adsorption-desorption curve.
Wherein, the curve of top represents that the curve of lower section in desorption curve, Fig. 1 represents adsorption curve in Fig. 1.
Fig. 2 is the highly acid solid acid catalyst sample of the load Loprazolam prepared in the present invention according to embodiment 1
Pore size distribution curve.
The characteristic X-ray diffracting spectrum (XRD) of Fig. 3 different samples obtained by the present invention.
Wherein：a：Pure silicon dioxide carrier；
b：The highly acid solid acid catalyst sample prepared according to embodiment 1；
c：The highly acid solid acid catalyst sample prepared according to embodiment 2.
Fig. 4 is the highly acid solid acid catalysis of the load Loprazolam prepared in the present invention according to embodiment 1 and embodiment 2
The catalyst catalytic performance curve using olefin removal rate as measurement index of agent sample.
Wherein a：The performance curve of the highly acid solid acid catalyst prepared using embodiment 1；
b：The performance curve of the highly acid solid acid catalyst prepared using embodiment 2.
Embodiment
The invention is further illustrated by the following examples.It is noted that without departing substantially from present subject matter and spirit
Under the conditions of, those of ordinary skill in the art can modify and change to specific embodiment.These modifications and variations
Fall in scope disclosed by the invention.
Embodiment 1：
Tetraethyl orthosilicate 21g and anhydrous formic acid 50g is added in stirred tank, stirs 30 minutes, is uniformly mixed molten
Liquid.Then Loprazolam 0.7g is added, stirring intensity is increased, continues to stir 50 minutes, forms catalyst intermediate.By what is obtained
Catalyst intermediate stands 6 hours at 30 DEG C, is then transferred in Muffle furnace, is calcined 6 hours, obtains at a temperature of 100 DEG C
To solid acid catalyst.
Solid acid catalyst sample is made in the present embodiment and carries out following evaluation：
(1)N2Adsorption-desorption isothermal curve,
(2) graph of pore diameter distribution,
(3) XRD.
The N of the gained solid acid catalyst sample of embodiment 12Adsorption-desorption isothermal curve, graph of pore diameter distribution, XRD difference
See Fig. 1-Fig. 3：
Wherein, its N2 adsorption-desorption isothermal curve illustrate catalyst prepared by embodiment 1 belong to it is international purely and application
Credit union of student's federation（IUPAC）The IV type physisorption isotherms of proposition.With the rise of relative pressure, catalyst occurs in duct
Capillary condensation phenomenon, catalyst surface can produce the multilayer absorption of gas.
Its graph of pore diameter distribution illustrates the aperture of catalyst prepared by embodiment 1 between 0.81-2.17nm, and 1.5nm is attached
Near duct proportion is larger.Reaction object can be moved freely in the catalyst with this pore passage structure, be reacted
Journey is not controlled by the size of reactant molecule.
Two curves of a in XRD, b show that the solid acid catalyst sample of embodiment 1 has pure (amorphous) titanium dioxide
Silicon carrier identical XRD features, show to load structure compared before the catalyst after Loprazolam and load and substantially do not change.
Embodiment 2：
Tetraethyl orthosilicate 21g and anhydrous formic acid 50g is added in stirred tank, stirs 30 minutes, is uniformly mixed molten
Liquid.Then Loprazolam 0.7g is added, stirring intensity is increased, continues to stir 50 minutes, forms catalyst intermediate.By what is obtained
Catalyst intermediate stands 6 hours at 30 DEG C, is then transferred in Muffle furnace, is calcined 6 hours, obtains at a temperature of 500 DEG C
To solid acid catalyst.
As described in Example 1, XRD evaluations are carried out to the gained solid acid catalyst of embodiment 2.
From Fig. 3 b, c curves are understood, the solid acid catalyst sample of embodiment 2 equally has pure (amorphous) titanium dioxide
Silicon carrier identical XRD features, show 100 DEG C in the catalyst and embodiment 1 after 500 DEG C of baked load Loprazolams
Catalyst after the load Loprazolam of roasting does not substantially change compared to silicon dioxide structure.That is, the skeleton structure of catalyst
500 DEG C of temperature can be born and be unlikely to avalanche.
Embodiment 3：
The solid acid catalyst 2ml of load Loprazolam prepared by Example 1 and embodiment 2, loads miniature fixed bed
In reactor, in 100 DEG C of temperature, pressure 1.0MPa, weight space velocity 30h-1Under conditions of, react 8 hours.Sampling point per hour
Analysis, sample bromine index is analyzed with bromine valency bromine index instrument.Catalyst catalytic performance curve using olefin removal rate as measurement index
See Fig. 4.
The figure shows that catalyst still has considerable catalytic performance after 500 DEG C are calcined, but is roasted relative to 100 DEG C
The catalyst catalytic performance of burning slightly declines.
Claims (13)
1. a kind of be used for the highly acid solid acid catalyst of olefin component in Arene removal, wherein, the highly acid solid acid is urged
Agent is in amorphous state, and includes Loprazolam amorphous silica and load thereon；The highly acid solid acid is urged
Agent is made in the following manner：
(1) in anhydrous conditions, tetraethyl orthosilicate (TEOS) and anhydrous formic acid are mixed, forms uniform solution；
(2) Loprazolam is added, continues to mix, forms catalyst intermediate；With
(3) catalyst intermediate is calcined, highly acid solid acid catalyst is formed.
2. it is used for the highly acid solid acid catalyst of olefin component in Arene removal as claimed in claim 1, it is characterised in that
The highly acid solid acid catalyst keeps original amorphous state after being calcined through 500 DEG C.
3. it is used for the highly acid solid acid catalyst of olefin component in Arene removal as claimed in claim 1, it is characterised in that
The specific surface area of the highly acid solid acid catalyst is 300-1000m2/ g, pore-size distribution is in 0.81-2.17nm.
4. a kind of prepare is used for the highly acid solid acid catalyst of olefin component in Arene removal described in claim any one of 1-3
Method, methods described includes：
(1) in anhydrous conditions, tetraethyl orthosilicate (TEOS) and anhydrous formic acid are mixed, forms uniform solution；
(2) Loprazolam is added, continues to mix, forms catalyst intermediate；With
(3) catalyst intermediate is calcined, highly acid solid acid catalyst is formed.
5. the method for the highly acid solid acid catalyst of olefin component in Arene removal is prepared as claimed in claim 4, its
It is characterised by, the tetraethyl orthosilicate (TEOS) and anhydrous formic acid mol ratio are 1：0.05-5.
6. the method for the highly acid solid acid catalyst of olefin component in Arene removal is prepared as claimed in claim 4, its
It is characterised by, in terms of the dry mass of amorphous silica, the amount of the Loprazolam is 1 mass %-30 mass %.
7. prepared as described in claim any one of 4-6 for the highly acid solid acid catalyst of olefin component in Arene removal
Method, it is characterised in that the catalyst intermediate stands 1-6 hours at 20-100 DEG C.
8. the method for the highly acid solid acid catalyst of olefin component in Arene removal is prepared as claimed in claim 7, its
It is characterised by, the catalyst intermediate stands 1-6 hours at 30 DEG C.
9. prepared as described in claim any one of 4-6 for the highly acid solid acid catalyst of olefin component in Arene removal
Method, it is characterised in that the catalyst intermediate is at a temperature of 60-500 DEG C in Muffle kiln roasting 1-6 hours.
10. the highly acid solid acid catalyst for olefin component in Arene removal is prepared as described in claim any one of 4-6
Method, it is characterised in that mixing tetraethyl orthosilicate (TEOS) and anhydrous formic acid carried out by stirring 30-100 minutes；
The stirring intensity for continuing mixing after Loprazolam is added higher than mixing tetraethyl orthosilicate (TEOS) and the stirring intensity of anhydrous formic acid.
11. the method for the highly acid solid acid catalyst of olefin component in Arene removal is prepared as claimed in claim 10,
Continue to mix 1-100 minutes characterized in that, adding after Loprazolam.
12. it is used for the highly acid solid acid catalyst of olefin component in Arene removal described in claim any one of 1-3 in aromatic hydrocarbons
Production in be used to remove the application of olefin component.
13. it is used for the highly acid solid acid catalyst of olefin component in Arene removal as claimed in claim 12 in paraxylene
It is used for the application for removing olefin component in production.
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| CN111825579A (en) * | 2020-07-23 | 2020-10-27 | 山东益丰生化环保股份有限公司 | Preparation method of pentaerythritol ester |
| CN114471704A (en) * | 2020-10-23 | 2022-05-13 | 华东理工大学 | Preparation of montmorillonite nanosheet loaded trifluoromethanesulfonic acid material and application of montmorillonite nanosheet loaded trifluoromethanesulfonic acid material in removal of trace olefins in aromatic hydrocarbons |
| CN113461944B (en) * | 2021-06-10 | 2023-01-06 | 佳化化学科技发展（上海）有限公司 | Solid acid and preparation method and application thereof |
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| JP4326265B2 (en) * | 2003-03-20 | 2009-09-02 | 昭和電工株式会社 | Solid acid catalyst |
| CN102600896A (en) * | 2012-01-20 | 2012-07-25 | 山东华阳油业有限公司 | Solid catalyst of bonded type organic sulfonic acid and its preparation method |
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Non-Patent Citations (3)
| Title |
|---|
| "二氧化硅负载甲烷磺酸催化酯交换制备生物柴油";任立国 等;《工业催化》;20091031;第17卷(第10期);摘要，第1.2节 * |
| Ying Tian et al."A Novel Application of Methanesulfonic Acid as Catalyst for the Alkylation of Olefins with Aromatics".《Ind. Eng. Chem. Res.》.2012,第51卷第2.2节，Figure 6，Figure 7. * |
| 章华桂."正硅酸乙酯的非水溶胶-凝胶反应与微滴乳液聚合法原位纳米复合".《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》.2012,(第2期),第1.1.2.2节，第2.2.2.2节，第2.3.1.1节，表2-3. * |
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