CN105903461A - Catalyst for synthesizing camphene and preparation method thereof - Google Patents
Catalyst for synthesizing camphene and preparation method thereof Download PDFInfo
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- CN105903461A CN105903461A CN201610260515.4A CN201610260515A CN105903461A CN 105903461 A CN105903461 A CN 105903461A CN 201610260515 A CN201610260515 A CN 201610260515A CN 105903461 A CN105903461 A CN 105903461A
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- amphene
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- titanium dioxide
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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 invention relates to a catalyst for synthesizing camphene; raw materials used for preparation include titanium dioxide, a weak acid, a metal chelating agent and water, wherein the titanium dioxide adopts titanium dioxide with the mass content of more than or equal to 99%, and the specific weight part ratios of the raw materials comprise 0.5-1.0 part of titanium dioxide, 0.6-2.0 parts of the weak acid, 0.005-0.01 part of the metal chelating agent, and 1.1-5.0 parts of water. The shortcomings that a conventional preparation process of a catalyst for synthesizing camphene has large consumption of raw materials in the preparation process, complicated process, more side reactions and low product yield are overcome; alkalis and strong acids are not required to be used in the preparation process, a large amount of water is not required to be consumed, the consumption amount of the raw materials can be greatly reduced, the technology process is simplified, the catalytic efficiency is high, and the product yield is high.
Description
Technical field
The present invention relates to a kind of for catalyst synthesizing amphene and preparation method thereof, apply and produce neck at amphene
Territory.
Background technology
Amphene is a kind of important industrial chemicals, is widely used in the synthesis such as spices, medicine field.Industrial camphane
Alkene is to be obtained by the main matter australene in isomerization turpentine oil, and device used catalyst has illiteracy de-
Stone, kaolin, cationic ion-exchange resin, molecular sieve, metatitanic acid etc..Current catalyst is the most partially
Metatitanic acid catalyst, such as shown in 201410066599.9, its reaction equation is as follows:
.Metatitanic acid catalyst is mainly by entering Ti-base catalyst (referring mainly to the pretreated titanium ores such as sulfuric acid)
Row alkali cleaning, pickling, be dried etc. operation prepare, have in preparation process adds various auxiliary agent to improve catalysis
The activity and selectivity of agent, such as aluminum oxide, zirconium oxide etc..Use the shortcoming that amphene prepared by metatitanic acid catalyst
It is: 1. preparation process needs to consume substantial amounts of alkali and strong acid, and needs washing step, at this washing step
In can produce substantial amounts of waste water, not only expend raw material and technical process be loaded down with trivial details；2. during the reaction of this catalyst
The side reaction existed is many, causes amphene yield on the low side.Therefore provide a kind of preparation process without expending alkali with strong
Acid, technical process is simple, and can save the water consumption in washing step, and in catalytic reaction, side reaction is few,
Efficiency of pcr product high for catalyst synthesizing amphene and preparation method thereof oneself become when business urgently.
Summary of the invention
Useless big in order to overcome the catalyst preparation section preparation process raw material of existing synthesis amphene to consume, technique is loaded down with trivial details,
And the shortcoming that side reaction is many, efficiency of pcr product is low, the present invention provide a kind of catalyst for synthesizing amphene and
Preparation method, its preparation process uses without using alkali and strong acid, without expending substantial amounts of water, has energy
Greatly reduce raw material consumption, simplify technical process, and the advantage that catalytic efficiency is high, efficiency of pcr product is high.
Technical scheme is as follows:
A kind of catalyst for synthesizing amphene, it prepares used raw material and includes: titanium dioxide, weak acid,
Metal-chelator and water, wherein titanium dioxide uses the titanium dioxide of mass content >=99%.
The weight ratio of described raw material is as follows:
It is currently used for synthesizing the metatitanic acid catalyst of the many uses of catalyst of amphene, pre-owing to using sulfuric acid etc.
The titanium ore processed is raw material, and it contains a large amount of metal impurities.Therefore, the preparation process of metatitanic acid catalyst
Need to use substantial amounts of alkali to wash foreign metal, but Actual laundering still remains more foreign metal, and
These metal impurities be cause that prepared metatitanic acid catalyst side reaction is many, reaction efficiency and the lowest
Main cause.And its preparation section also needs to use strong acid to carry out acidification, it is therefore desirable to substantial amounts of water
Wash, thus produce substantial amounts of waste water.The catalyst being used for synthesizing amphene of the application then selects to contain
The titanium dioxide that impurity is few is raw material, and auxiliary adds metal-chelator, and minimizing removal washing impurity is required to be used
Water consumption, coordinate weak acid treatment to regulate acidity of catalyst center to improve its selectivity simultaneously, not only protect
Demonstrate,prove the efficient and high selectivity of catalyst, also greatly reduce the water consumption of washing step.The application's is new
The formula of type catalyst, preparation technology is simple, alkali need not be used to process and strong acid treatment, can be greatly reduced former
The usage amount of material, energy-conserving and environment-protective again while ensureing catalyst premium properties.
Described weak acid is any combination of any one or more in boric acid, acetic acid, succinic acid, citric acid, profit
In promoting the catalytic performances such as the efficiency of catalyst, selectivity.
Described metal-chelator is ethylenediamine tetra-acetic acid, and preferred metal-chelator can promote in removal titanium dioxide
The ability of impurity.
Described water is deionized water.
The weight ratio of described raw material is as follows:
This preferred raw material and proportioning make the catalyst prepared have catalytic efficiency and the selectivity of optimum.
The preparation method of the described catalyst for synthesizing amphene, including following preparation process:
1. after being sequentially added into described titanium dioxide, weak acid, metal-chelator, water and stirring reaction 4-8h,
It is filtrated to get sediment；
2. add water to sediment, and pH value is controlled at 3-6, after stirring 2-8h, be again filtrated to get
Sediment；
3. sediment is put into drying box, 80-120 DEG C of dry 4-8h, after then taking out grinding, continues to put
Entering drying box, 80-120 DEG C of dry 4-8h i.e. prepares amphene.
Currently used metatitanic acid catalyst reaction side reaction is many, and the low reason of amphene yield is except by gold
Belonging to impurity and cause outside side reaction, metal impurities exist and preparation technology is (main on the impact of the surface texture of catalyst
The composition structure of catalyst to be affected, the specific surface area of catalyst surface and the distribution of its acid centre) be also
One of the main reasons.Existing metatitanic acid catalyst uses high-temperature calcination in preparation process more, not only consumes energy but also right
The surface texture of catalyst has a significant impact so that catalytic efficiency and the selectivity of metatitanic acid catalyst are the highest.
And the application controls to be acidified pH value by strict in the preparation technology of the catalyst synthesizing amphene, at acid
Reason regulates acid centre to change selectivity, complex reaction time and the control of relatively low baking temperature simultaneously
Prepare efficient and high selective catalyst.
Described step 1. with step 2. in the weight ratio that added water be 6:5-3:2.
Described step 1. middle mixing time is 5h；Step 2. middle pH value is 3.5, and mixing time is 6h；Step
3. twice baking temperature in is 100 DEG C, and twice drying time is 6h.Preferably reaction time, acid
Change that pH value and baking temperature make to prepare for synthesizing the catalyst efficiency of amphene, the most optimal.
Compared with prior art, the present patent application has the advantage that
1) with titanium dioxide as raw material, auxiliary is added metal-chelator and is improved existing amphene synthesis technique,
And then reach the purpose of process simplification, process without alkali and i.e. can remove foreign metal；
2) using weak acid to be acidified and control higher pH value in its preparation process, therefore, slurry amount can be significantly
Reduce, energy-saving and emission-reduction；
3) by strict acidifying pH value, reaction time and the relatively low baking temperature controlled in catalytic synthesis
(80-120 DEG C), controls the surface texture of catalyst, thus prepares selective catalysis efficient, high
Agent, and more energy efficient.
Detailed description of the invention
Below technical scheme is described in detail.
Raw material information:
Boric acid, succinic acid, citric acid: analyze pure；
Acetic acid: mass concentration is more than 99%；
Titanium dioxide (mass content >=99%): chemical pure.
Embodiment 1
The preparation method of a kind of catalyst for synthesizing amphene of the present invention includes following preparation process:
1. 1kg titanium dioxide (mass content >=99%), 1.2kg boric acid, 0.01kg second two it are sequentially added into
Amine tetraacethyl, 2kg deionized water and stir reaction 4h after, be filtrated to get sediment；
2. add 1.8kg deionized water to sediment, and pH value is controlled 5.6, after stirring 4h, then
Secondary it is filtrated to get sediment；
3. sediment is put into 120 DEG C of dry 4h of drying box, after then taking out grinding, continues to put into dry
120 DEG C of dry 4h of case i.e. prepare amphene.
Embodiment 2
The preparation method of a kind of catalyst for synthesizing amphene of the present invention includes following preparation process:
1. 1kg titanium dioxide (mass content >=99%), 1.4kg acetic acid, 0.008kg second two it are sequentially added into
Amine tetraacethyl, 2.8kg deionized water and stir reaction 5h after, be filtrated to get sediment；
2. add 2.0kg deionized water to sediment, and pH value is controlled 3.5, after stirring 6h, then
Secondary it is filtrated to get sediment；
3. sediment is put into 100 DEG C of dry 6h of drying box, after then taking out grinding, continues to put into dry
100 DEG C of dry 6h of case i.e. prepare amphene.
Embodiment 3
The preparation method of a kind of catalyst for synthesizing amphene of the present invention includes following preparation process:
1. 1kg titanium dioxide (mass content >=99%), 1.2kg succinic acid, 0.01kg second it are sequentially added into
Ethylenediamine tetraacetic acid (EDTA), 2.6kg deionized water and stir reaction 8h after, be filtrated to get sediment；
2. add 0.5kg deionized water to sediment, and pH value is controlled 4.8, after stirring 8h, then
Secondary it is filtrated to get sediment；
3. sediment is put into 90 DEG C of dry 8h of drying box, after then taking out grinding, continues to put into drying box
90 DEG C of dry 8h i.e. prepare amphene.
Embodiment 4
The preparation method of a kind of catalyst for synthesizing amphene of the present invention includes following preparation process:
1. 1kg titanium dioxide (mass content >=99%), 1.4kg citric acid, 0.006kg second it are sequentially added into
Ethylenediamine tetraacetic acid (EDTA), 2.8kg deionized water and stir reaction 8h after, be filtrated to get sediment；
2. add 1.5kg deionized water to sediment, and pH value is controlled 4.3, after stirring 8h, then
Secondary it is filtrated to get sediment；
3. sediment is put into 110 DEG C of dry 5h of drying box, after then taking out grinding, continues to put into dry
110 DEG C of dry 5h of case i.e. prepare amphene.
Embodiment 5
The preparation method of a kind of catalyst for synthesizing amphene of the present invention includes following preparation process:
1. 0.5kg titanium dioxide (mass content >=99%), 1.4kg boric acid, 0.6kg vinegar it are sequentially added into
Acid, 0.005kg metal-chelator, 0.6kg water and stir reaction 6h after, be filtrated to get sediment；
2. add 0.5kg deionized water to sediment, and pH value is controlled 3, after stirring 2h, again
It is filtrated to get sediment；
3. sediment is put into 80 DEG C of dry 5h of drying box, after then taking out grinding, continues to put into drying box
80 DEG C of dry 8h i.e. prepare amphene.
Embodiment 6
The preparation method of a kind of catalyst for synthesizing amphene of the present invention includes following preparation process:
1. 0.8kg titanium dioxide (mass content >=99%), 0.2kg boric acid, 0.3kg fourth it are sequentially added into
Diacid, 0.006kg metal-chelator, 2.5kg water and stir reaction 5h after, be filtrated to get sediment；
2. add 0.8kg deionized water to sediment, and pH value is controlled 5, after stirring 6h, again
It is filtrated to get sediment；
3. sediment is put into 80 DEG C of dry 5h of drying box, after then taking out grinding, continues to put into drying box
100 DEG C of dry 6h i.e. prepare amphene.
Embodiment 7
The preparation method of a kind of catalyst for synthesizing amphene of the present invention includes following preparation process:
1. 0.9kg titanium dioxide (mass content >=99%), 0.3kg boric acid, 0.5kg lemon it are sequentially added into
Lemon acid, 0.008kg metal-chelator, 3.0kg water and stir reaction 6h after, be filtrated to get sediment；
2. add 2.0kg deionized water to sediment, and pH value is controlled 6, after stirring 8h, again
It is filtrated to get sediment；
3. sediment is put into 90 DEG C of dry 6h of drying box, after then taking out grinding, continues to put into drying box
120 DEG C of dry 8h i.e. prepare amphene.
Embodiment 8
The preparation method of a kind of catalyst for synthesizing amphene of the present invention includes following preparation process:
It uses the mixture of acetic acid and succinic acid, this weak acid with the weak acid that is in raw material of difference implementing 5
Total usage amount be 0.6-2.0kg.
Embodiment 9
The preparation method of a kind of catalyst for synthesizing amphene of the present invention includes following preparation process:
It uses the mixture of acetic acid and citric acid, this weak acid with the weak acid that is in raw material of difference implementing 6
Total usage amount be 0.6-2.0kg.
Embodiment 10
The preparation method of a kind of catalyst for synthesizing amphene of the present invention includes following preparation process:
It uses the mixture of succinic acid and citric acid with the weak acid that is in raw material of difference implementing 7, and this is weak
Total usage amount of acid is 0.6-2.0kg.
Embodiment 11
The preparation method of a kind of catalyst for synthesizing amphene of the present invention includes following preparation process:
It uses the mixture of boric acid, acetic acid and succinic acid with the weak acid that is in raw material of difference implementing 5,
Total usage amount of this weak acid is 0.6-2.0kg.
Embodiment 12
The preparation method of a kind of catalyst for synthesizing amphene of the present invention includes following preparation process:
It uses the mixture of boric acid, acetic acid and citric acid with the weak acid that is in raw material of difference implementing 6,
Total usage amount of this weak acid is 0.6-2.0kg.
Embodiment 13
The preparation method of a kind of catalyst for synthesizing amphene of the present invention includes following preparation process:
It uses the mixture of acetic acid, succinic acid and citric acid with the weak acid that is in raw material of difference implementing 7,
Total usage amount of this weak acid is 0.6-2.0kg.
Embodiment 14
The preparation method of a kind of catalyst for synthesizing amphene of the present invention includes following preparation process:
Its weak acid being in raw material with the difference implementing 5 uses boric acid, acetic acid, succinic acid and citric acid
Mixture, total usage amount of this weak acid is 0.6-2.0kg.
The catalyst of each embodiment and the properties contrast table of the metatitanic acid catalyst of use in prior art
As seen from the above table, the selectivity of the catalyst of the application is above the catalyst reported at present, conversion ratio
All close to even more than its optimal value.Wherein, with the catalyst performance for synthesizing amphene of embodiment 2
Good.Visible, the application not only simplify preparation section for catalyst synthesizing amphene and preparation method thereof,
Energy-saving and emission-reduction, and the catalytic effect of product catalyst is excellent.
Of the present invention a kind of not only it is limited only to for catalyst synthesizing amphene and preparation method thereof
Above-described embodiment, every any improvement according to the principle of the invention or replacement, all should be at the protection model of the present invention
Within enclosing.
Claims (9)
1. the catalyst being used for synthesizing amphene, it is characterised in that: it is prepared used raw material and includes:
Titanium dioxide, weak acid, metal-chelator and water, wherein titanium dioxide uses the titanium dioxide of mass content >=99%
Titanium.
Catalyst for synthesizing amphene the most according to claim 1, it is characterised in that: described raw material
Weight ratio as follows:
Catalyst for synthesizing amphene the most according to claim 1, it is characterised in that: described weak acid
For any combination of any one or more in boric acid, acetic acid, succinic acid, citric acid.
Catalyst for synthesizing amphene the most according to claim 3, it is characterised in that: described metal
Chelating agent is ethylenediamine tetra-acetic acid.
Catalyst for synthesizing amphene the most according to claim 4, it is characterised in that: described water is
Deionized water.
Catalyst for synthesizing amphene the most according to claim 5, it is characterised in that: described raw material
Weight ratio as follows:
7. according to the preparation method of the catalyst for synthesizing amphene described in any one of claim 1-6, its
It is characterised by: include following preparation process:
1. after being sequentially added into described titanium dioxide, weak acid, metal-chelator, water and stirring reaction 4-8h,
It is filtrated to get sediment；
2. add water to sediment, and pH value is controlled at 3-6, after stirring 2-8h, be again filtrated to get
Sediment；
3. sediment is put into drying box, 80-120 DEG C of dry 4-8h, after then taking out grinding, continues to put
Entering drying box, 80-120 DEG C of dry 4-8h i.e. prepares amphene.
The preparation method of the catalyst for synthesizing amphene the most according to claim 7, it is characterised in that:
Described step 1. with step 2. in the weight ratio that added water be 6:5-3:2.
The preparation method of the catalyst for synthesizing amphene the most according to claim 7, it is characterised in that:
Described step 1. middle mixing time is 5h；Step 2. middle pH value is 3.5, and mixing time is 6h；Step 3. in
Twice baking temperature be 100 DEG C, twice drying time is 6h.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610260515.4A CN105903461B (en) | 2016-04-25 | 2016-04-25 | It is a kind of to be used to synthesize catalyst of amphene and preparation method thereof |
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| CN201610260515.4A CN105903461B (en) | 2016-04-25 | 2016-04-25 | It is a kind of to be used to synthesize catalyst of amphene and preparation method thereof |
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Citations (4)
| 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 |
| WO2012052209A1 (en) * | 2010-10-22 | 2012-04-26 | Crenox Gmbh | Supported catalyst of digestion residues of titanyl sulphate-containing black solution |
-
2016
- 2016-04-25 CN CN201610260515.4A patent/CN105903461B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1118499A (en) * | 1966-04-13 | 1968-07-03 | Le Lesotekh Akad | Method of preparing camphene |
| WO2012052209A1 (en) * | 2010-10-22 | 2012-04-26 | Crenox Gmbh | Supported catalyst of digestion residues of titanyl sulphate-containing black solution |
| 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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Effective date of registration: 20200115 Address after: 354200 No. 85 Tower Road, Hui Yao Industrial Park, Jianyang District, Nanping, Fujian Patentee after: Fujian Nanping green pine Chemical Co., Ltd. Address before: 354200 Yao Yao Industrial Park, Jianyang District, Fujian, Nanping Patentee before: Fujian Green Pine Co., Ltd. |