CN105903461B - It is a kind of to be used to synthesize catalyst of amphene and preparation method thereof - Google Patents
It is a kind of to be used to synthesize catalyst of amphene and preparation method thereof Download PDFInfo
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- CN105903461B CN105903461B CN201610260515.4A CN201610260515A CN105903461B CN 105903461 B CN105903461 B CN 105903461B CN 201610260515 A CN201610260515 A CN 201610260515A CN 105903461 B CN105903461 B CN 105903461B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
- C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
- C07C5/29—Rearrangement of carbon atoms in the hydrocarbon skeleton changing the number of carbon atoms in a ring while maintaining the number of rings
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Abstract
The present invention relates to a kind of for synthesizing the catalyst of amphene, raw material used in preparation includes：Titanium dioxide, weak acid, metal-chelator and water, wherein titanium dioxide use the titanium dioxide of mass content >=99%, and the weight ratio of specific raw material is as follows：0.5 1.0 parts of titanium dioxide, 0.6 2.0 parts of weak acid, 0.005 0.01 parts of metal-chelator, 1.1 5.0 parts of water.The invention overcomes the catalyst preparation process preparation process raw material consumption of existing synthesis amphene useless big, technique is cumbersome, and the shortcomings that side reaction is more, efficiency of pcr product is low, its preparation process use is without using alkali and strong acid, without a large amount of water of consuming, with raw material consumption can be greatly reduced, technical process is simplified, and high catalytic efficiency, the advantages of efficiency of pcr product is high.
Description
Technical field
The present invention relates to a kind of for synthesizing catalyst of amphene and preparation method thereof, apply in amphene production field.
Background technology
Amphene is a kind of important industrial chemicals, is widely used in the synthesis such as fragrance, drug field.Industrial amphene is to pass through
Main matter australene in isomerization turpentine oil and obtain, device used catalyst has montmorillonite, kaolin, cation exchange
Resin, molecular sieve, metatitanic acid etc..Catalyst at present is mainly metatitanic acid catalyst, such as shown in 201410066599.9,
Its reaction equation is as follows：
.Metatitanic acid catalyst to Ti-base catalyst (referring mainly to the pretreated titanium ore such as sulfuric acid) mainly by carrying out alkali
Wash, pickling, the processes such as drying are made, there is some in preparation process adds various auxiliary agents to improve the activity of catalyst and selection
Property, such as aluminium oxide, zirconium oxide.It is using the shortcomings that metatitanic acid catalyst preparation amphene：1. preparation process needs to consume big
The alkali and strong acid of amount, and washing step is needed, a large amount of waste water can be generated in the washing step, not only expends raw material and technique
Process is cumbersome；2. existing side reaction is more when the catalyst reacts, cause amphene yield relatively low.Therefore a kind of prepare is provided
Process need not expend alkali and strong acid, and technical process is simple, and can save the water consumption in washing step, and be catalyzed secondary in reaction
Reaction is few, efficiency of pcr product it is high for synthesize catalyst of amphene and preparation method thereof oneself become when business urgently.
Invention content
In order to overcome the catalyst preparation process preparation process raw material consumption of existing synthesis amphene useless big, technique is cumbersome, and secondary
The shortcomings that reaction is more, efficiency of pcr product is low, the present invention provide a kind of for synthesizing catalyst of amphene and preparation method thereof, preparation
Process use is without using alkali and strong acid, and without a large amount of water is expended, raw material consumption can be greatly reduced by having, and simplify work
Skill process, and high catalytic efficiency, the advantages of efficiency of pcr product is high.
Technical scheme is as follows：
A kind of catalyst for being used to synthesize amphene, raw material used in preparation include：Titanium dioxide, weak acid, metal chelating
Mixture and water, wherein titanium dioxide use the titanium dioxide of mass content >=99%.
The weight ratio of the raw material is as follows：
Currently used for the metatitanic acid catalyst that the catalyst for synthesizing amphene uses more, due to using pretreatments such as sulfuric acid
The titanium ore crossed is raw material, contains a large amount of metal impurities.Therefore, the preparation process of metatitanic acid catalyst needs to use a large amount of alkali
Wash foreign metal, but more foreign metal is still remained in Actual laundering, and the metal impurities be cause it is prepared inclined
The main reason for metatitanic acid catalyst side reaction is more, reaction efficiency and selectivity are low.And it is also needed in its preparation section using strong
Acid carries out acidification, it is therefore desirable to which a large amount of water is washed, so as to generate a large amount of waste water.And the application for synthesizing
It is raw material that the catalyst of amphene, which then selects impure few titanium dioxide, and it is miscellaneous to reduce removal washing for auxiliary addition metal-chelator
The water consumption used needed for matter, while coordinate weak acid treatment to adjust acidity of catalyst center to improve its selectivity, not only protect
The efficient and highly selective of catalyst has been demonstrate,proved, has also greatly reduced the water consumption of washing step.The new catalyst of the application
Formula, preparation process is simple, and without alkali process and strong acid treatment is used, the usage amount of raw material can be greatly reduced, and is ensureing to be catalyzed
While agent excellent performance again energy conservation and environmental protection.
The weak acid is the arbitrary combination of boric acid, acetic acid, succinic acid, citric acid any one or more of, conducive to promotion
The catalytic performances such as efficiency, the selectivity of catalyst.
The metal-chelator is ethylenediamine tetra-acetic acid, and preferred metal-chelator can promote impurity in removal titanium dioxide
Ability.
The water is deionized water.
The weight ratio of the raw material is as follows：
The preferred raw material and proportioning are so that the catalyst prepared has optimal catalytic efficiency and selectivity.
The preparation method of the catalyst for being used to synthesize amphene, including following preparation process：
1. sequentially adding the titanium dioxide, weak acid, metal-chelator, water and after being stirred to react 4-8h, it is heavy to be obtained by filtration
Starch；
2. water is added in, and sediment is obtained by filtration after 3-6, stirring 2-8h in pH value control again to sediment；
3. sediment is put into drying box, 80-120 DEG C of dry 4-8h after then taking out grinding, continues to be put into drying box,
80-120 DEG C of dry 4-8h obtains amphene.
The reason of metatitanic acid catalyst reaction side reaction used at present is more, and amphene yield is low are in addition to by metal impurities
Cause outside side reaction, the influence of metal impurities presence and preparation process to the surface texture of catalyst be (main influence catalyst
Form structure, the specific surface area of catalyst surface and the distribution of its acid centre) it is also one of the main reasons.Existing metatitanic acid is urged
Agent, mostly using high-temperature calcination, had not only consumed energy but also had had a significant impact to the surface texture of catalyst so that inclined titanium in preparation process
The catalytic efficiency and selectivity of acid catalyst be not high.And the application is used in the preparation process of catalyst for synthesizing amphene by tight
Lattice control acidification pH value changes selectivity with acid processing to adjust acid centre, while complex reaction time and relatively low
Efficient and highly selective catalyst is prepared in the control of drying temperature.
The step 1. with step 2. in added water weight ratio be 6:5-3:2.
1. middle mixing time is 5h to the step；2. middle pH value is 3.5 to step, mixing time 6h；Step 3. in two
Secondary drying temperature is 100 DEG C, and drying time is 6h twice.Preferred reaction time, acidification pH value and drying temperature cause
That prepares is best for synthesizing the catalyst efficiency of amphene, selectivity.
Compared with prior art, the present patent application has the following advantages：
1) using titanium dioxide as raw material, auxiliary addition metal-chelator is improved existing amphene synthesis technology, into
And achieve the purpose that process simplification, it can remove foreign metal without alkali process；
2) it is acidified in its preparation process using weak acid and controls higher pH value, therefore, slurry amount can be greatly decreased,
Energy-saving and emission-reduction；
3) by strictly controlling acidification pH value, reaction time and relatively low drying temperature (80- in catalytic synthesis
120 DEG C), to control the surface texture of catalyst, so as to prepare efficient, highly selective catalyst, and it is more energy efficient.
Specific embodiment
Technical scheme of the present invention is described in detail below.
Raw material information：
Boric acid, succinic acid, citric acid：It analyzes pure；
Acetic acid：Mass concentration is more than 99%；
Titanium dioxide (mass content >=99%)：Chemistry is pure.
Embodiment 1
A kind of preparation method of catalyst for being used to synthesize amphene of the present invention includes following preparation process：
1. sequentially add 1kg titanium dioxide (mass content >=99%), 1.2kg boric acid, 0.01kg ethylenediamine tetra-acetic acids,
2kg deionized waters and after being stirred to react 4h, are obtained by filtration sediment；
2. 1.8kg deionized waters are added in sediment, and by pH value control after 5.6, stirring 4h, it is heavy to be obtained by filtration again
Starch；
3. sediment is put into the dry 4h of 120 DEG C of drying box, after then taking out grinding, it is dry to continue to be put into 120 DEG C of drying box
Dry 4h obtains amphene.
Embodiment 2
A kind of preparation method of catalyst for being used to synthesize amphene of the present invention includes following preparation process：
1. sequentially add 1kg titanium dioxide (mass content >=99%), 1.4kg acetic acid, 0.008kg ethylenediamine tetra-acetic acids,
2.8kg deionized water and after being stirred to react 5h, is obtained by filtration sediment；
2. 2.0kg deionized waters are added in sediment, and by pH value control after 3.5, stirring 6h, it is heavy to be obtained by filtration again
Starch；
3. sediment is put into the dry 6h of 100 DEG C of drying box, after then taking out grinding, it is dry to continue to be put into 100 DEG C of drying box
Dry 6h obtains amphene.
Embodiment 3
A kind of preparation method of catalyst for being used to synthesize amphene of the present invention includes following preparation process：
1. sequentially add 1kg titanium dioxide (mass content >=99%), 1.2kg succinic acid, 0.01kg ethylenediamine tetra-acetic acids,
2.6kg deionized waters and after being stirred to react 8h, are obtained by filtration sediment；
2. 0.5kg deionized waters are added in sediment, and by pH value control after 4.8, stirring 8h, it is heavy to be obtained by filtration again
Starch；
3. sediment is put into the dry 8h of 90 DEG C of drying box, after then taking out grinding, continue to be put into 90 DEG C of dryings of drying box
8h obtains amphene.
Embodiment 4
A kind of preparation method of catalyst for being used to synthesize amphene of the present invention includes following preparation process：
1. sequentially add 1kg titanium dioxide (mass content >=99%), 1.4kg citric acids, 0.006kg ethylenediamine tetrems
Acid, 2.8kg deionized waters and after being stirred to react 8h, are obtained by filtration sediment；
2. 1.5kg deionized waters are added in sediment, and by pH value control after 4.3, stirring 8h, it is heavy to be obtained by filtration again
Starch；
3. sediment is put into the dry 5h of 110 DEG C of drying box, after then taking out grinding, it is dry to continue to be put into 110 DEG C of drying box
Dry 5h obtains amphene.
Embodiment 5
A kind of preparation method of catalyst for being used to synthesize amphene of the present invention includes following preparation process：
1. sequentially add 0.5kg titanium dioxide (mass content >=99%), 1.4kg boric acid, 0.6kg acetic acid, 0.005kg gold
Belong to chelating agent, 0.6kg water and after being stirred to react 6h, sediment is obtained by filtration；
2. 0.5kg deionized waters are added in, and precipitation is obtained by filtration after 3, stirring 2h in pH value control again to sediment
Object；
3. sediment is put into the dry 5h of 80 DEG C of drying box, after then taking out grinding, continue to be put into 80 DEG C of dryings of drying box
8h obtains amphene.
Embodiment 6
A kind of preparation method of catalyst for being used to synthesize amphene of the present invention includes following preparation process：
1. sequentially add 0.8kg titanium dioxide (mass content >=99%), 0.2kg boric acid, 0.3kg succinic acid, 0.006kg
Metal-chelator, 2.5kg water and after being stirred to react 5h, are obtained by filtration sediment；
2. 0.8kg deionized waters are added in, and precipitation is obtained by filtration after 5, stirring 6h in pH value control again to sediment
Object；
3. sediment is put into the dry 5h of 80 DEG C of drying box, after then taking out grinding, continue to be put into 100 DEG C of dryings of drying box
6h obtains amphene.
Embodiment 7
A kind of preparation method of catalyst for being used to synthesize amphene of the present invention includes following preparation process：
1. sequentially add 0.9kg titanium dioxide (mass content >=99%), 0.3kg boric acid, 0.5kg citric acids, 0.008kg
Metal-chelator, 3.0kg water and after being stirred to react 6h, are obtained by filtration sediment；
2. 2.0kg deionized waters are added in, and precipitation is obtained by filtration after 6, stirring 8h in pH value control again to sediment
Object；
3. sediment is put into the dry 6h of 90 DEG C of drying box, after then taking out grinding, continue to be put into 120 DEG C of dryings of drying box
8h obtains amphene.
Embodiment 8
A kind of preparation method of catalyst for being used to synthesize amphene of the present invention includes following preparation process：Itself and reality
Applying 5, difference lies in the mixtures that the weak acid in raw material uses acetic acid and succinic acid, and total usage amount of the weak acid is 0.6-
2.0kg。
Embodiment 9
A kind of preparation method of catalyst for being used to synthesize amphene of the present invention includes following preparation process：Itself and reality
Applying 6, difference lies in the mixtures that the weak acid in raw material uses acetic acid and citric acid, and total usage amount of the weak acid is 0.6-
2.0kg。
Embodiment 10
A kind of preparation method of catalyst for being used to synthesize amphene of the present invention includes following preparation process：Itself and reality
7 are applied difference lies in the mixture that the weak acid in raw material uses succinic acid and citric acid, total usage amount of the weak acid is
0.6-2.0kg。
Embodiment 11
A kind of preparation method of catalyst for being used to synthesize amphene of the present invention includes following preparation process：Itself and reality
5 are applied difference lies in the mixture that the weak acid in raw material uses boric acid, acetic acid and succinic acid, total usage amount of the weak acid is
0.6-2.0kg。
Embodiment 12
A kind of preparation method of catalyst for being used to synthesize amphene of the present invention includes following preparation process：Itself and reality
6 are applied difference lies in the mixture that the weak acid in raw material uses boric acid, acetic acid and citric acid, total usage amount of the weak acid is
0.6-2.0kg。
Embodiment 13
A kind of preparation method of catalyst for being used to synthesize amphene of the present invention includes following preparation process：Itself and reality
Applying 7, difference lies in the mixture that the weak acid in raw material uses acetic acid, succinic acid and citric acid, total usage amounts of the weak acid
For 0.6-2.0kg.
Embodiment 14
A kind of preparation method of catalyst for being used to synthesize amphene of the present invention includes following preparation process：Itself and reality
5 are applied difference lies in the mixture that the weak acid in raw material uses boric acid, acetic acid, succinic acid and citric acid, the weak acid it is total
Usage amount is 0.6-2.0kg.
The catalyst of each embodiment and the properties contrast table of metatitanic acid catalyst used in the prior art
As seen from the above table, the selectivity of the catalyst of the application is above the catalyst reported at present, and conversion ratio is all close
Even more than its optimal value.Wherein, it is best for synthesizing the catalyst performance of amphene with embodiment 2.As it can be seen that the application is used for
Catalyst for synthesizing amphene and preparation method thereof not only simplifies the catalysis effect of preparation section, energy-saving and emission-reduction, and product catalyst
Fruit is excellent.
It is of the present invention it is a kind of for synthesize catalyst of amphene and preparation method thereof be not only limited only to it is above-mentioned
Embodiment, any improvement or replacement of every principle according to the present invention, should all be within protection scope of the present invention.
Claims (6)
1. a kind of catalyst for being used to synthesize amphene, it is characterised in that：Raw material used in its preparation includes：It is titanium dioxide, weak
Acid, metal-chelator and water, wherein titanium dioxide use the titanium dioxide of mass content >=99%；
The weight ratio of the raw material is as follows：
0.5-1.0 parts of titanium dioxide
0.6-2.0 parts of weak acid
0.005-0.01 parts of metal-chelator
1.1-5.0 parts of water；
The weak acid is the arbitrary combination of boric acid, acetic acid, succinic acid, citric acid any one or more of；
The metal-chelator is ethylenediamine tetra-acetic acid；
The preparation method of the catalyst for being used to synthesize amphene, including following preparation process：
1. sequentially adding the titanium dioxide, weak acid, metal-chelator, water and after being stirred to react 4-8h, sediment is obtained by filtration；
2. water is added in, and sediment is obtained by filtration after 3-6, stirring 2-8h in pH value control again to sediment；
3. sediment is put into drying box, 80-120 DEG C of dry 4-8h after then taking out grinding, continues to be put into drying box, 80-
120 DEG C of dry 4-8h obtain the catalyst of synthesis amphene.
2. the catalyst according to claim 1 for being used to synthesize amphene, it is characterised in that：The water is deionized water.
3. the catalyst according to claim 2 for being used to synthesize amphene, it is characterised in that：The weight ratio of the raw material
It is as follows：
1.0 parts of titanium dioxide
1.4 parts of acetic acid
0.008 part of ethylenediamine tetra-acetic acid
4.8 parts of deionized water.
4. it is used to synthesize the preparation method of the catalyst of amphene according to claim 1-3 any one of them, it is characterised in that：Packet
Include following preparation process：
1. sequentially adding the titanium dioxide, weak acid, metal-chelator, water and after being stirred to react 4-8h, sediment is obtained by filtration；
2. water is added in, and sediment is obtained by filtration after 3-6, stirring 2-8h in pH value control again to sediment；
3. sediment is put into drying box, 80-120 DEG C of dry 4-8h after then taking out grinding, continues to be put into drying box, 80-
120 DEG C of dry 4-8h obtain the catalyst of synthesis amphene.
5. the preparation method of the catalyst according to claim 4 for being used to synthesize amphene, it is characterised in that：The step is 1.
With step 2. in added water weight ratio be 6:5-3:2.
6. the preparation method of the catalyst according to claim 4 for being used to synthesize amphene, it is characterised in that：The step is 1.
Middle mixing time is 5h；2. middle pH value is 3.5 to step, mixing time 6h；Step 3. in drying temperature twice be 100
DEG C, drying time is 6h twice.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1118499A (en) * | 1966-04-13 | 1968-07-03 | Le Lesotekh Akad | Method of preparing camphene |
| CN102126904A (en) * | 2011-01-20 | 2011-07-20 | 大连理工大学 | Method for isomerizing alpha-pinene |
| CN102343277A (en) * | 2011-06-30 | 2012-02-08 | 大连理工大学 | High performance alpha-pinene isomerization catalyst and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2444150A1 (en) * | 2010-10-22 | 2012-04-25 | crenox GmbH | Carrier catalyst consisting of pulp remnants of black solution containing titanyl sulfate |
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2016
- 2016-04-25 CN CN201610260515.4A patent/CN105903461B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1118499A (en) * | 1966-04-13 | 1968-07-03 | Le Lesotekh Akad | Method of preparing camphene |
| CN102126904A (en) * | 2011-01-20 | 2011-07-20 | 大连理工大学 | Method for isomerizing alpha-pinene |
| CN102343277A (en) * | 2011-06-30 | 2012-02-08 | 大连理工大学 | High performance alpha-pinene isomerization catalyst and application thereof |
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