CN101138731A - Load type heteropoly compound catalyzer for interesterification synthesis reacting - Google Patents
Load type heteropoly compound catalyzer for interesterification synthesis reacting Download PDFInfo
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- CN101138731A CN101138731A CNA2006101128370A CN200610112837A CN101138731A CN 101138731 A CN101138731 A CN 101138731A CN A2006101128370 A CNA2006101128370 A CN A2006101128370A CN 200610112837 A CN200610112837 A CN 200610112837A CN 101138731 A CN101138731 A CN 101138731A
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- catalyst
- carbonate
- heteropoly compound
- compound
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Abstract
The present invention relates to a supported heteropoly compound catalyst used for an ester exchange synthesis reaction and is in particular applicable for a reaction to synthesize alkyl aryl carbonate (for example, methyl phenyl carbonate) and diaryl carbonate (for example, diphenyl carbonate) through the ester exchange of dialkyl carbonates (for example, dimethyl carbonate) and aromatic phenolic compound (for example, phenol). The catalyst uses a supported heteropoly compound as an active component, and a mulit-pore material as a carrier to make the total yield ratio reach 46 percent, and the selectivity reach 99 percent. Moreover, the catalyst is provided with the advantage that the catalyst is environment-friendly, causes no corrosion to the equipment, and can be separated easily, the preparation is simple, and so on.
Description
Technical field
The present invention relates to a kind of loaded catalyst, particularly a kind of supported heteropoly compound catalyst.
Background technology
Diaryl carbonate (particularly diphenyl carbonate) is a kind of important organic synthesis intermediate, not only is used for products such as synthetic medicine, agricultural chemicals, and is the important intermediate of preparation Merlon, has very high industrial value.The synthetic method of diaryl carbonate mainly contains phosgenation, ester-interchange method and phenolic compound oxidative carbonylation method etc.
Because the phosgene severe toxicity, so phosgenation can cause serious environmental to pollute, and just progressively eliminated.Though phenolic compound oxidative carbonylation method raw material is simple and easy to, atom utilization is also higher, and its employed catalyst costliness and catalytic efficiency are not high, make the use of this method be restricted.Ester-interchange method is to adopt a kind of phenolic compound (for example phenol, methylphenol, xylenol etc.) and a kind of dialkyl carbonate (as dimethyl carbonate, diethyl carbonate) under catalyst action, reaction generates a kind of green synthetic route of diaryl carbonate, the methyl alcohol of Sheng Chenging can be used as the raw material of green Synthesis of dimethyl carbonate simultaneously, these two reacting phase combinations can form the green building-up process of " zero-emission ".Ester-interchange method mainly adopts homogeneous phase and heterogeneous two kinds of catalyst.
Reaction with dimethyl carbonate and phenol ester exchange synthesizing diphenyl carbonate is an example, and this reaction is the thermodynamics reversible reaction, and the equilibrium constant is very little (to be 3 * 10 during 453K
-4), be unfavorable for the generation of target product, make that the yield of diphenyl carbonate is low, reaction speed is also very slow.Problems such as ester-interchange method diphenyl carbonate synthesis technology mainly exists equilibrium yield low at present, and existing catalyst price is more expensive, efficient is high inadequately.
The catalyst of phenolic compound and dialkyl carbonate ester exchange carbonate synthesis diaryl mostly is homogeneous catalyst.JP56-25138 adopts alkali or alkali metal compound catalyst, and reaction speed is slow, and the diphenyl carbonate productive rate is low and a large amount of CO arranged
2Generate with methyl phenyl ethers anisole.DE2528412 and JP63-92662 adopt lewis acid catalyst, as AlX
3, ZnX
3, FeX
3, TiX
3, TiX
4, SnX
4Deng (wherein X is halogen, alkoxyl, acetoxyl group or aryloxy group), the diphenyl carbonate productive rate slightly improves, but the severe corrosive of catalyst has brought difficulty to industrialization.The catalyst that DE344552, JP63-92662, EP780361 adopt in the reaction of ester exchange synthesizing diphenyl carbonate is the organic compound of Sn and Ti, as Dibutyltin oxide [(C
4H
9)
2SnO], butyl titanate [Ti (OC
4H
9)
4], metatitanic acid phenyl ester [Ti (OPh)
4] or butyl tin trichloride [C
4H
9SnCl
3] etc., effect is better, but catalyst separates and recycles with product and have difficulties, and the catalyst price is more expensive.
It is higher that homogeneous catalyst is produced the diaryl carbonate productive rate, but problems such as difficulty and contaminated environment are separated, reclaimed to general the existence.
JP09-241217 has studied the heterogeneous micropore catalyst that contains IV family metal, and the yield of methyl benzol carbonate and diphenyl carbonate is respectively 11.5% and 0.2%; JP09-241218 adopt titanium, iron respectively with the mixed oxide catalyst of IIIB family metal, the diphenyl carbonate yield is respectively 13.6% and 8.5%.
Fu and Ono (Z-H.Fu and Y.Ono, J.Mol.Catal.A:Chemical, 118 (1997): 293) studied support type MoO
3, Ga
2O
3, V
2O
5, PbO, ZrO
2, TiO
2, Cr
2O
3, MgO, Mn
3O
4, NiO etc. is to the catalytic activity of dimethyl carbonate and phenol ester exchange synthesizing diphenyl carbonate, finds MoO
3/ SiO
2Active best, the total recovery of methyl benzol carbonate and diphenyl carbonate is 17.3%, wherein the yield of methyl benzol carbonate is 17.1%.Won Bae Kim and Jae Sung Lee (W.S.Kim, J.S.Lee.Catal Lett, 59 (1999): be carrier 83), studied molybdenum, titanium, vanadium, the chromium of support type, the catalytic performance of tungsten metal oxidic catalyst, TiO with active carbon, silica and titanium dioxide
2/ SiO
2Activity of such catalysts is the highest, and phenol conversion is 37.2% in gas-phase reaction, and the yield of methyl benzol carbonate and diphenyl carbonate is respectively 31.7% and 1.7%.
CN1394679 is the reaction that catalyst carries out ester exchange synthesizing diphenyl carbonate with lead oxide-zinc oxide composite metal oxide, and the yield of diphenyl carbonate is up to 45.6%, selectivity 72%.(Org.Process Res.Dev. such as F.M.Mei, 2003,8 (3): 372) adopt the Mg-Al hydrotalcite catalyst to study the reaction of ester exchange synthesizing diphenyl carbonate, the conversion ratio of dimethyl carbonate is 31.9%, the total recovery of methyl benzol carbonate and diphenyl carbonate is 26.3%, and the ester exchange selectivity is up to 82%.
CN1669655 is used for synthesis of diphenyl carbonate by ester exchange reaction with solid heteropoly acid salt catalyzer, its heteropolyacid salt is in conjunction with normal salt that forms or acid salt by the Keggin structure heteropoly acid of one or both coordination atoms and metal ion or ammonium ion, this catalyst has activity and selectivity preferably to dimethyl carbonate and the reaction of phenol ester exchange synthesizing diphenyl carbonate, phenol conversion reaches 30%, the ester exchange selectivity reaches 99%, but this catalyst cost is higher, form suspension with product, not easily separated, there is certain difficulty in catalyst recovery.
Summary of the invention
The objective of the invention is to overcome in the prior art that the interesterification synthesis yield is low, catalyst separation reclaims problems such as difficulty, a kind of new supported heteropoly compound catalyst that is used for interesterification synthesis is provided.
A kind of supported heteropoly compound catalyst that is used for interesterification synthesis provided by the present invention, its carrier is SiO
2, Al
2O
3, TiO
2, porous material such as MgO, bentonite, diatomite, molecular sieve or active carbon, active component is the heteropoly compound that contains the Keggin structure of one or both coordination atoms, said heteropoly compound is heteropoly acid or heteropolyacid salt.The anion structure of heteropoly compound is [XM
12O
40]
N-Or [XM
12-mV
mO
40]
N-(X=P or Si, or As, or Ge; M=Mo or W); The cation of heteropoly compound is H
+, NH
4 +, or Li
+, Na
+, K
+, Rb
+, Cs
+, Be
2+, Mg
2+, Ca
2+, Sr
2+, Ba
2+Deng alkali metal or alkaline-earth metal ions, or Cu
2+, Ag
+, Zn
2+, Fe
3+, Ni
2+Deng I B-VIIIB family metal ion, or Al
3+, pb
2+In one or more.
The load capacity of the said heteropoly compound of the present invention is 5～70%, is preferably 10～45% (quality percentage compositions).
Supported heteropoly compound catalyst of the present invention is to make with conventional infusion process, and heteropoly acid can be buied from market, and heteropolyacid salt can be made by neutralization reaction or metathesis reaction by heteropoly acid and corresponding alkali or salt.
Catalyst of the present invention is applicable to interesterification synthesis, is particularly useful for the reaction by dialkyl carbonate and phenolic compound ester exchange synthesis of alkyl aryl carbonates and diaryl carbonate.Dialkyl carbonate can be dimethyl carbonate, diethyl carbonate etc.; Phenolic compound can be the phenol that is replaced by one or more substituting groups on phenol, naphthols or the aromatic ring, and substituting group can be CH
3, CH
3CH
2, NO
2, among F, Cl, Br, CN, RO etc. one or more.
Catalyst provided by the present invention has following characteristics:
(1) catalyst activity height.Solid catalyst of the present invention has good activity to the reaction of ester-interchange method synthesis of alkyl aryl carbonates and diaryl carbonate, and especially the reaction to ester-interchange method carbonate synthesis diaryl has good active.When being used for dimethyl carbonate and phenol ester exchange synthesis of methyl phenyl carbonic ester and diphenyl carbonate, the gross production rate of its methyl benzol carbonate and diphenyl carbonate is up to 46.5%, and overall selectivity can reach 99%, and activity and selectivity are significantly better than other heterogeneous catalysis.
(2) catalyst is easy to separate and reclaims.Homogeneous catalyst exists product to separate, reclaim problems such as difficulty, because catalyst provided by the invention is a solid catalyst, is insoluble to reactant mixture, therefore very easily separates with product.
(3) etching apparatus not, free from environmental pollution.
(4) Preparation of Catalyst is simple.
The specific embodiment
Embodiment 1
1. take into account in the there-necked flask of rectifying column in that wireway and temperature are housed, add 3 gram SiO
2Molybdovanaphosphoric acid (the H of load
4PMo
11VO
40/ SiO
2) catalyst (load capacity is 10%).
2. under the nitrogen protection, add phenol 15 grams.
, when being heated to 178 ℃, (be called for short: DMC), the total amount that adds DMC is 13.5ml to begin to add dimethyl carbonate.Pick up counting from adding DMC, reacted 8 hours, constantly steam the mixed fraction of methyl alcohol and dimethyl carbonate in the course of reaction by rectifying column.
4. analyze mixed fraction and the reactant liquor that contains principal product methyl benzol carbonate and diphenyl carbonate with Tianjin, island GC-14B gas chromatograph, normalization method is quantitative with proofreading and correct, record: the conversion ratio of phenol is 19.3%, and the productive rate of methyl benzol carbonate and diphenyl carbonate is respectively 12.3% and 6.7%.
Embodiment 2-embodiment 10
Reaction condition and analysis test method are with embodiment 1, and reaction result sees Table 1.
The catalytic activity of table 1 embodiment 2-embodiment 10 catalyst
| Embodiment | Catalyst | Load capacity (%) | Catalyst amount (gram) | Phenol conversion (%) | Productive rate (%) | |
| MPC | DPC | |||||
| Embodiment 2 | Cu 3/2PMo 12O 40/SiO 2 | 12 | 1.5 | 20.5 | 12.8 | 7.5 |
| Embodiment 3 | H 3PMo 12O 40/ active carbon | 15 | 2.0 | 21.2 | 9.9 | 11.3 |
| Embodiment 4 | Mg 3/2PMo 12O 40/ Ti molecular sieve | 18 | 2.0 | 30.0 | 14.5 | 11.5 |
| Embodiment 5 | Pb 3/2PMo 10V 2O 40/ molecular sieve | 35 | 2.0 | 25.6 | 13.0 | 11.8 |
| Embodiment 6 | Li 3PMo 12O 40/TiO 2 | 15 | 2.0 | 33.1 | 14.5 | 18.0 |
| Embodiment 7 | H 3PMo 12O 40/TiO 2 | 25 | 1.5 | 47.1 | 22.5 | 24.0 |
| Embodiment 8 | K mH 4-mSiW 12O 40/MgO | 15 | 1.5 | 23.2 | 12.4 | 8.1 |
| Embodiment 9 | AlPW 12O 40/Al 2O 3 | 45 | 1.5 | 37.4 | 20.8 | 15.3 |
| Embodiment 10 | Na 5SiMo 11VO 40/SiO 2 | 20 | 2.0. | 21.2 | 11.5 | 7.0 |
*MPC: methyl benzol carbonate; DPC: diphenyl carbonate.
Claims (7)
1. supported heteropoly compound catalyst that is used for interesterification synthesis, its carrier is SiO
2, Al
2O
3, TiO
2, MgO, bentonite, diatomite, molecular sieve or active carbon, active component is the heteropoly compound that contains the Keggin structure of one or both coordination atoms.
2. according to the catalyst of claim 1, it is characterized in that heteropoly compound wherein is heteropoly acid or heteropolyacid salt.
3. according to the catalyst of claim 1, the anion structure that it is characterized in that heteropoly compound wherein is [XM
12O
40]
N-Or [XM
12-mV
mO
40]
N-(X=P or Si, or As, or Ge; M=Mo or W); Cation is H
+, NH
4 +, alkali metal or alkaline-earth metal ions, or I B-VIIIB family metal ion, or Al
3+, Pb
2+In one or more.
4. according to the catalyst of claim 3, it is characterized in that wherein alkali metal or alkaline-earth metal ions are Li
+, Na
+, K
+, Rb
+, Cs
+, Be
2+, Mg
2+, Ca
2+, Sr
2+, Ba
2+, or IB-VIIIB family metal ion is Cu
2+, Ag
+, Zn
2+, Fe
3+, Ni
2+
5. according to the catalyst of claim 1, the mass percent that it is characterized in that the load capacity of heteropoly compound wherein is 5～70%.
6. according to the catalyst of claim 1, the mass percent that it is characterized in that the load capacity of heteropoly compound wherein is 10～45%.
7. according to the catalyst of claim 1, it is characterized in that wherein interesterification synthesis is the reaction by dialkyl carbonate and phenolic compound ester exchange synthesis of alkyl aryl carbonates and diaryl carbonate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2006101128370A CN101138731A (en) | 2006-09-05 | 2006-09-05 | Load type heteropoly compound catalyzer for interesterification synthesis reacting |
Applications Claiming Priority (1)
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|---|---|---|---|
| CNA2006101128370A CN101138731A (en) | 2006-09-05 | 2006-09-05 | Load type heteropoly compound catalyzer for interesterification synthesis reacting |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101138731A true CN101138731A (en) | 2008-03-12 |
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ID=39190932
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|---|---|---|---|
| CNA2006101128370A Pending CN101138731A (en) | 2006-09-05 | 2006-09-05 | Load type heteropoly compound catalyzer for interesterification synthesis reacting |
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|---|---|
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102773115A (en) * | 2012-08-02 | 2012-11-14 | 江苏丹化煤制化学品工程技术有限公司 | Supported catalyst for diphenyl carbonate synthesis by reaction of phenylacetate and dimethyl carbonate and preparation method thereof |
| CN103012153A (en) * | 2012-12-16 | 2013-04-03 | 青岛森淼实业有限公司 | Application of catalyst in ester-exchanging synthesis reaction |
| CN103012127A (en) * | 2011-09-28 | 2013-04-03 | 中国石油化工股份有限公司 | Method for subjecting phenol and dimethyl ester to transesterification |
| CN103191782A (en) * | 2012-01-09 | 2013-07-10 | 爱普香料集团股份有限公司 | Supported solid acid catalyst, and method for preparing ester perfumes through applying it |
| CN107029692A (en) * | 2016-01-25 | 2017-08-11 | 中国科学院成都有机化学有限公司 | A kind of preparation method of ester exchange synthesizing diphenyl carbonate CNT Quito phase catalyst |
| CN107915638A (en) * | 2016-10-08 | 2018-04-17 | 中国石油化工股份有限公司 | The method for producing dimethyl carbonate |
| CN107915572A (en) * | 2016-10-08 | 2018-04-17 | 中国石油化工股份有限公司 | The method of ester exchange Synthesis of dimethyl carbonate |
| CN109675621A (en) * | 2017-10-19 | 2019-04-26 | 中国石油化工股份有限公司 | Composite catalyst preparation and application for diphenyl carbonate preparation |
| CN110295068A (en) * | 2018-11-29 | 2019-10-01 | 湖北工业大学 | Utilize the method for Catalyzed by Heteropolyacid Supported on Actived Carbon agent biodiesel synthesis |
| CN112705183A (en) * | 2019-10-24 | 2021-04-27 | 中国石油化工股份有限公司 | Catalyst for preparing diphenyl carbonate and preparation method and application thereof |
-
2006
- 2006-09-05 CN CNA2006101128370A patent/CN101138731A/en active Pending
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103012127B (en) * | 2011-09-28 | 2015-08-26 | 中国石油化工股份有限公司 | A kind of phenol and dimethyl ester carry out the method for transesterify |
| CN103012127A (en) * | 2011-09-28 | 2013-04-03 | 中国石油化工股份有限公司 | Method for subjecting phenol and dimethyl ester to transesterification |
| CN103191782B (en) * | 2012-01-09 | 2015-08-26 | 爱普香料集团股份有限公司 | Load-type solid acid catalyst and be applied to the method preparing ester perfume |
| CN103191782A (en) * | 2012-01-09 | 2013-07-10 | 爱普香料集团股份有限公司 | Supported solid acid catalyst, and method for preparing ester perfumes through applying it |
| CN102773115B (en) * | 2012-08-02 | 2015-10-07 | 江苏丹化煤制化学品工程技术有限公司 | A kind of loaded catalyst for phenylacetate and dimethyl carbonate diphenyl carbonate synthesis and preparation method thereof |
| CN102773115A (en) * | 2012-08-02 | 2012-11-14 | 江苏丹化煤制化学品工程技术有限公司 | Supported catalyst for diphenyl carbonate synthesis by reaction of phenylacetate and dimethyl carbonate and preparation method thereof |
| CN103012153A (en) * | 2012-12-16 | 2013-04-03 | 青岛森淼实业有限公司 | Application of catalyst in ester-exchanging synthesis reaction |
| CN107029692A (en) * | 2016-01-25 | 2017-08-11 | 中国科学院成都有机化学有限公司 | A kind of preparation method of ester exchange synthesizing diphenyl carbonate CNT Quito phase catalyst |
| CN107915638A (en) * | 2016-10-08 | 2018-04-17 | 中国石油化工股份有限公司 | The method for producing dimethyl carbonate |
| CN107915572A (en) * | 2016-10-08 | 2018-04-17 | 中国石油化工股份有限公司 | The method of ester exchange Synthesis of dimethyl carbonate |
| CN107915572B (en) * | 2016-10-08 | 2021-02-09 | 中国石油化工股份有限公司 | Method for synthesizing dimethyl carbonate by ester exchange |
| CN107915638B (en) * | 2016-10-08 | 2021-02-09 | 中国石油化工股份有限公司 | Method for producing dimethyl carbonate |
| CN109675621A (en) * | 2017-10-19 | 2019-04-26 | 中国石油化工股份有限公司 | Composite catalyst preparation and application for diphenyl carbonate preparation |
| CN110295068A (en) * | 2018-11-29 | 2019-10-01 | 湖北工业大学 | Utilize the method for Catalyzed by Heteropolyacid Supported on Actived Carbon agent biodiesel synthesis |
| CN112705183A (en) * | 2019-10-24 | 2021-04-27 | 中国石油化工股份有限公司 | Catalyst for preparing diphenyl carbonate and preparation method and application thereof |
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