CN108043465A - A kind of preparation method for the catalyst and acetic acid for synthesizing acetic acid - Google Patents
A kind of preparation method for the catalyst and acetic acid for synthesizing acetic acid Download PDFInfo
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- CN108043465A CN108043465A CN201711365950.4A CN201711365950A CN108043465A CN 108043465 A CN108043465 A CN 108043465A CN 201711365950 A CN201711365950 A CN 201711365950A CN 108043465 A CN108043465 A CN 108043465A
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2217—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
- C07C51/12—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on an oxygen-containing group in organic compounds, e.g. alcohols
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/04—Indoles; Hydrogenated indoles
- C07D209/10—Indoles; Hydrogenated indoles with substituted hydrocarbon radicals attached to carbon atoms of the hetero ring
- C07D209/18—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D209/20—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals substituted additionally by nitrogen atoms, e.g. tryptophane
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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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/827—Iridium
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of preparation methods for the catalyst and acetic acid for synthesizing acetic acid.The catalyst is the ion centered on iridium, using β indolylalanines as complex made of ligand；The preparation method of acetic acid is：1）The catalyst and methanol, ruthenic chloride, iodomethane are fitted into reaction kettle, and are sufficiently mixed；2）It seals reaction kettle and uses the air in carbon monoxide replacement reaction kettle, adjust the pressure in reaction kettle, it is made to react to acetic synthesis reaction kettle heating and finished；3）After reaction stops, by reaction kettle cooled to room temperature；4）Reaction kettle is opened, catalyst, ruthenic chloride, iodomethane, by-product methyl acetate and water is isolated with the way of distillation, obtains acetic acid.The present invention has the characteristics of can reducing side reaction, improving reaction effect, and can reduce production cost.
Description
Technical field
The present invention relates to a kind of preparation methods for the catalyst and acetic acid for synthesizing acetic acid, particularly a kind of methanol carbonylation
Produce the catalyst of acetic acid and the preparation method of acetic acid.
Background technology
It is extremely wide as a kind of purposes of important industrial chemicals acetic acid (CH3COOH), for example, for synthetic fibers, coating,
The industry such as medicine, pesticide, food additives, dyeing and weaving.In the method for preparing acetic acid, methanol carbonylation is in catalyst action
Under, acetic acid is made by catalytic reaction in autoclave in material benzenemethanol (CH3OH) and carbon monoxide (CO).Methanol carbonyl
The mainstream catalyst that base method uses at present is the rhodium base catalyst that Mansanto companies of the U.S. successfully develop and the iridium of BP companies
Base catalyst, but they separate difficulty after catalytic reaction with product, easily cause catalyst member loss.It is lacked for these
Point, domestic and international researcher constantly explore some new catalyst system and catalyzings and/or new process, on the one hand, ring is added in catalyst system and catalyzing
The solvent of border close friend or stabilizer-ionic liquid, make catalyst make it easy to separate and recycle in low-steam pressure.On the other hand, grind
The composition catalyst for sending out new is to reach separating catalyst, the purpose of high efficiente callback.
However, in these methods of application ionic liquid, some side reactions but increased；It is some larger there are energy consumption
The problem of, and because ionic liquid is added in cost is increased.For example, ZL 201110376456.4, entitled《It is a kind of
The method that acetic acid is prepared with methanol carbonylation》, to reduce side reaction to the greatest extent or to ensure reaction effect, having resulted in reaction
The higher deficiency of system totle drilling cost.
The content of the invention
It is an object of the present invention to provide a kind of preparation methods for the catalyst and acetic acid for synthesizing acetic acid.The present invention has
The characteristics of side reaction can be reduced, reaction effect is improved, and production cost can be reduced.
Technical scheme：A kind of catalyst for synthesizing acetic acid, is the ion centered on iridium, with the third ammonia of β-indyl
Acid is complex made of ligand；Its preparation method includes the following steps：
1) tryptophane is dissolved in absolute ethyl alcohol, obtains A product；
2) iridous chloride is dissolved in absolute ethyl alcohol, obtains B product；
3) under nitrogen protection and stirring, A product are added in B product, flows back 30-60 minutes in 80-100 DEG C, obtains C
Product；
4) C product are cooled to room temperature, then adding in excessive ether makes it precipitate completely, filtering, and obtaining target after dry urges
Agent.
The catalyst of foregoing synthesis acetic acid in the step 3), is flowed back 45 minutes at 90 DEG C.
The catalyst of foregoing synthesis acetic acid, in the step 3), when A product are mixed with B product, tryptophane and three
The molar ratio of iridium chloride is 1:3.
A kind of method of the catalyst preparation acetic acid of foregoing synthesis acetic acid, step include：
1) catalyst and methanol, ruthenic chloride, iodomethane are fitted into reaction kettle, and are sufficiently mixed；
2) seal reaction kettle and use the air in carbon monoxide replacement reaction kettle, adjust reaction kettle in pressure, to react
Kettle heating finishes its reaction to acetic synthesis；
3) after reaction stops, by reaction kettle cooled to room temperature；
4) reaction kettle is opened, catalyst, ruthenic chloride, iodomethane, by-product methyl acetate and water is isolated with the way of distillation, obtains
Acetic acid.
The preparation method of foregoing acetic acid, in the step 1), by weight, the reaction system in reaction kettle includes
35-50 parts of methanol, catalyst are the 1000-2000ppm of the reaction system weight, and the weight of contained ruthenium is catalyst in ruthenic chloride
In 4-6 times of weight of contained iridium, surplus is iodomethane.
The preparation method of foregoing acetic acid, by weight, the reaction system in the reaction kettle include 43 parts of methanol,
Catalyst is the 1500ppm of the reaction system weight, and the weight of contained ruthenium is 5 of the weight of contained iridium in catalyst in ruthenic chloride
Times, surplus is iodomethane.
The preparation method of foregoing acetic acid, described in the step 2), the pressure in reaction kettle is 2.5-3.5MPa, is risen
Temperature is 130-160 DEG C.
The preparation method of foregoing acetic acid, the pressure in the reaction kettle are 3MPa, and warming temperature is 145 DEG C.
Beneficial effects of the present invention：
1st, as can be seen that employing catalyst --- the tryptophane complex of iridium of the present invention from scheme
Afterwards, and according to the method for the present invention come when using acetic acid synthesis from methanol carbonylation, the maximum temperature of reaction is also only 160 DEG C, with showing
There is technology is minimum will compare at 170 DEG C, save the energy, reduce cost.
2nd, for the present invention due to not adding water and other Organic chemical solvents again in the reactant of synthesis acetic acid, these are anti-
Other reaction raw materials amounts can correspondingly be increased again by answering the reduction of raw material, and finally obtain more product, further reduce body
The cost of system.Further, since tryptophane complex of iridium, which has, stablizes N → Ir coordinate bonds, and O → Ir coordinate bonds, catalysis
The stability of agent is strong, and therefore, the catalyst amount of can be recycled is larger, is also very easy to separate with product.Verification shows with this
When invention catalyst and its method synthesis acetic acid, also have the advantages of methanol conversion, acetic acid selectivity and higher acetic acid yield,
The generation of side reaction is greatly reduced, improves reaction effect.
In short, the present invention had both had the advantages of side reaction is few, and reaction effect is good, and have the advantages that production cost is low.
Experimental example：
Synthetic catalyst：Heating temperature is respectively adopted 80 DEG C, 90 DEG C and 100 DEG C, and return time has been used 45 minutes, institute
Obtain the yield of catalyst tryptophane complex of iridium, average out to 93.8%.
Synthesize acetic acid：The step of acetic acid is synthesized during experiment is identical with step of the present invention, and reaction kettle used accords with for pressure
Close the reaction kettle of requirement.When step (4) opens reaction kettle, in the product without finding precipitation --- this illustrates catalysis of the present invention
Agent, afterwards without result in inactivation, is still stable by catalytic reaction.After step (4) obtains acetic acid, with GC-4000A gas
Chromatograph instrument, selects Porapak-Q stainless stee l packed columns, and thermal conductivity cell detector analyzes the product after purification.
Then methanol conversion, acetic acid selectivity and acetic acid yield are calculated.
Verification result be shown in the following table [in table, only list each distinguishing project of example parameter, unlisted project with this
As invention is disclosed.In addition, to compare influence of the other element to effect, the reaction time in reaction kettle takes 2 small
When].
Table 1：Add in the verification example of accelerating agent ruthenic chloride
From table 1 it follows that the present invention in maximum temperature (160 DEG C) than prior art minimum response temperature (170
DEG C) also want low 10 DEG C in the case of, methanol conversion, acetic acid selectivity and acetic acid yield etc. are higher.This also illustrates the present invention
Ionic liquid used can strengthen the effect of catalyst of the present invention.Also, with acetic acid selectively compared with, by-product methyl acetate
With the selectivity of water is relatively low namely the yield of principal product acetic acid can preferably be ensured；Obviously, using acetic acid yield as
It is only when pursuing a goal, reaction temperature choose 160 DEG C it is more preferable.
To the catalyst of recycling, identical verification four times is repeated, verification result is as follows：
Table 2：Catalyst re-uses four times
In table 2, for number 1 to use for the first time, number 2,3,4,5 is reuse.From Table 2, it can be seen that β-indoles
Base alanine iridium complex catalyst in the present invention, also with preferable stability, it is being used by 5 Xun Huan catalysis
Afterwards, catalytic activity is without being decreased obviously；The selectivity of by-product methyl acetate and water is remained on than relatively low.
Description of the drawings
Attached drawing 1 is the structural formula of complex.
Specific embodiment
With reference to embodiment, the present invention is further illustrated, but is not intended as the foundation limited the present invention.
The embodiment of the present invention
Embodiment 1：A kind of catalyst for synthesizing acetic acid, is the ion centered on iridium, using tryptophane as ligand
Manufactured complex；Its preparation methods steps are as follows：
1) tryptophane is dissolved in absolute ethyl alcohol, obtains A product；
2) iridous chloride is dissolved in absolute ethyl alcohol, obtains B product；
3) under nitrogen protection and stirring, A product are added in B product, flows back 45 minutes in 90 DEG C, obtains C product, wherein A
When product are mixed with B product, the molar ratio of tryptophane and iridous chloride is 1:3；
4) C product are cooled to room temperature, then adding in excessive ether makes it precipitate completely, filtering, and obtaining target after dry urges
Agent.
Embodiment 2：A kind of catalyst for synthesizing acetic acid, is the ion centered on iridium, using tryptophane as ligand
Manufactured complex；Its preparation methods steps are as follows：
1) tryptophane is dissolved in absolute ethyl alcohol, obtains A product；
2) iridous chloride is dissolved in absolute ethyl alcohol, obtains B product；
3) under nitrogen protection and stirring, A product are added in B product, flows back 60 minutes in 80 DEG C, obtains C product, wherein A
When product are mixed with B product, the molar ratio of tryptophane and iridous chloride is 1:3；
4) C product are cooled to room temperature, then adding in excessive ether makes it precipitate completely, filtering, and obtaining target after dry urges
Agent.
Embodiment 3：A kind of catalyst for synthesizing acetic acid, is the ion centered on iridium, using tryptophane as ligand
Manufactured complex；Its preparation methods steps are as follows：
1) tryptophane is dissolved in absolute ethyl alcohol, obtains A product；
2) iridous chloride is dissolved in absolute ethyl alcohol, obtains B product；
3) under nitrogen protection and stirring, A product are added in B product, flows back 30 minutes in 100 DEG C, obtains C product, wherein A
When product are mixed with B product, the molar ratio of tryptophane and iridous chloride is 1:3；
4) C product are cooled to room temperature, then adding in excessive ether makes it precipitate completely, filtering, and obtaining target after dry urges
Agent.
Embodiment 4：A kind of method using above-mentioned catalyst preparation acetic acid, step are as follows：
1) above-mentioned catalyst and methanol, ruthenic chloride, iodomethane are fitted into reaction kettle, and are sufficiently mixed, wherein, by weight
Part meter, the reaction system in reaction kettle include 43 parts of methanol, and catalyst is the 1500ppm of the reaction system weight, ruthenic chloride
In the weight of contained ruthenium be 5 times of the weight of contained iridium in catalyst, surplus is iodomethane；
2) seal reaction kettle and use the air in carbon monoxide replacement reaction kettle, adjust reaction kettle in pressure be 3MPa,
145 DEG C are heated to reaction kettle, finishes its reaction to acetic synthesis；
3) after reaction stops, by reaction kettle cooled to room temperature；
4) reaction kettle is opened, catalyst, ruthenic chloride, iodomethane, by-product methyl acetate and water is isolated with the way of distillation, obtains
Acetic acid.
Embodiment 5：A kind of method using above-mentioned catalyst preparation acetic acid, step are as follows：
1) above-mentioned catalyst and methanol, ruthenic chloride, iodomethane are fitted into reaction kettle, and are sufficiently mixed, wherein, by weight
Part meter, the reaction system in reaction kettle include 35 parts of methanol, and catalyst is the 1000ppm of the reaction system weight, ruthenic chloride
In the weight of contained ruthenium be 4 times of the weight of contained iridium in catalyst, surplus is iodomethane；
2) reaction kettle is sealed and with the air in carbon monoxide replacement reaction kettle, the pressure adjusted in reaction kettle is
2.5MPa is heated to reaction kettle 130 DEG C, finishes its reaction to acetic synthesis；
3) after reaction stops, by reaction kettle cooled to room temperature；
4) reaction kettle is opened, catalyst, ruthenic chloride, iodomethane, by-product methyl acetate and water is isolated with the way of distillation, obtains
Acetic acid.
Embodiment 6：A kind of method using above-mentioned catalyst preparation acetic acid, step are as follows：
1) above-mentioned catalyst and methanol, ruthenic chloride, iodomethane are fitted into reaction kettle, and are sufficiently mixed, wherein, by weight
Part meter, the reaction system in reaction kettle include 50 parts of methanol, and catalyst is the 2000ppm of the reaction system weight, ruthenic chloride
In the weight of contained ruthenium be 6 times of the weight of contained iridium in catalyst, surplus is iodomethane；
2) reaction kettle is sealed and with the air in carbon monoxide replacement reaction kettle, the pressure adjusted in reaction kettle is
3.5MPa is heated to reaction kettle 160 DEG C, finishes its reaction to acetic synthesis；
3) after reaction stops, by reaction kettle cooled to room temperature；
4) reaction kettle is opened, catalyst, ruthenic chloride, iodomethane, by-product methyl acetate and water is isolated with the way of distillation, obtains
Acetic acid.
Claims (8)
1. a kind of catalyst for synthesizing acetic acid, it is characterised in that：It is the ion centered on iridium, using tryptophane as ligand
Manufactured complex；Its preparation method includes the following steps：
1）Tryptophane is dissolved in absolute ethyl alcohol, obtains A product；
2）Iridous chloride is dissolved in absolute ethyl alcohol, obtains B product；
3）Under nitrogen protection and stirring, A product are added in B product, flows back 30-60 minutes in 80-100 DEG C, obtains C product；
4）C product are cooled to room temperature, then adding in excessive ether makes it precipitate completely, filtering, and final catalyst is obtained after dry.
2. the catalyst of synthesis acetic acid according to claim 1, it is characterised in that：The step 3）In, it is to be returned at 90 DEG C
Stream 45 minutes.
3. the catalyst of synthesis acetic acid according to claim 1, it is characterised in that：The step 3）In, A product are mixed with B product
During conjunction, the molar ratio of tryptophane and iridous chloride is 1:3.
4. a kind of method of catalyst preparation acetic acid using such as claim 1-3 any one of them synthesis acetic acid, feature
It is, step includes：
1）The catalyst and methanol, ruthenic chloride, iodomethane are fitted into reaction kettle, and are sufficiently mixed；
2）Seal reaction kettle and use the air in carbon monoxide replacement reaction kettle, the pressure in adjustment reaction kettle, to reaction kettle plus
Heat finishes its reaction to acetic synthesis；
3）After reaction stops, by reaction kettle cooled to room temperature；
4）Reaction kettle is opened, catalyst, ruthenic chloride, iodomethane, by-product methyl acetate and water is isolated with the way of distillation, obtains vinegar
Acid.
5. the preparation method of acetic acid according to claim 4, it is characterised in that：The step 1）In, by weight, instead
The reaction system in kettle is answered to include 35-50 parts of methanol, catalyst is the 1000-2000 ppm of the reaction system weight, chlorination
The weight of contained ruthenium is 4-6 times of the weight of contained iridium in catalyst in ruthenium, and surplus is iodomethane.
6. the preparation method of acetic acid according to claim 5, it is characterised in that：By weight, in the reaction kettle
Reaction system includes 43 parts of methanol, and catalyst is 1500 ppm of the reaction system weight, the weight of contained ruthenium in ruthenic chloride
For 5 times of the weight of contained iridium in catalyst, surplus is iodomethane.
7. the preparation method of acetic acid according to claim 4, it is characterised in that：It is described in the step 2）In, reaction kettle
Interior pressure is 2.5-3.5MPa, and warming temperature is 130-160 DEG C.
8. the preparation method of acetic acid according to claim 7, it is characterised in that：Pressure in the reaction kettle is 3MPa,
Warming temperature is 145 DEG C.
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| CN201711365950.4A CN108043465A (en) | 2017-12-18 | 2017-12-18 | A kind of preparation method for the catalyst and acetic acid for synthesizing acetic acid |
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| CN201711365950.4A CN108043465A (en) | 2017-12-18 | 2017-12-18 | A kind of preparation method for the catalyst and acetic acid for synthesizing acetic acid |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114134186A (en) * | 2021-11-04 | 2022-03-04 | 河北维达康生物科技有限公司 | Method for synthesizing 5-hydroxy beta-indolyl alanine by using glucose as substrate through biological method |
-
2017
- 2017-12-18 CN CN201711365950.4A patent/CN108043465A/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114134186A (en) * | 2021-11-04 | 2022-03-04 | 河北维达康生物科技有限公司 | Method for synthesizing 5-hydroxy beta-indolyl alanine by using glucose as substrate through biological method |
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Application publication date: 20180518 |