CN103896749A - Method used for preparation of methyl aldehyde and co-production of methylal - Google Patents
Method used for preparation of methyl aldehyde and co-production of methylal Download PDFInfo
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- CN103896749A CN103896749A CN201210571082.6A CN201210571082A CN103896749A CN 103896749 A CN103896749 A CN 103896749A CN 201210571082 A CN201210571082 A CN 201210571082A CN 103896749 A CN103896749 A CN 103896749A
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- catalyst
- dme
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/48—Preparation of compounds having groups
- C07C41/50—Preparation of compounds having groups by reactions producing groups
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
The invention provides a method used for preparation of methyl aldehyde and co-production of methylal by oxidizing dimethyl ether. According to the method, raw material gas containing dimethyl ether and oxygen passes through a reactor filled with a double phase catalyst, and reaction is carried out at a reaction temperature of 250 to 400 DEG C, under a reaction pressure of 0.1 to 0.5MPa, and with gaseous hourly space velocity of 1000 to 10000/h so as to realize preparation of methyl aldehyde and co-production of methylal, wherein the double phase catalyst comprises a molybdenum and/or vanadium-based oxide catalyst I and a solid acid catalyst II, and the balance is inert gas which is used as a diluent gas; molar content of dimethyl ether accounts for 3 to 25% of that of the raw material gas, molar content of oxygen accounts for 10.0 to 40.0%.
Description
Technical field
The present invention relates to a kind of method of preparing formaldehyde coproduction methylal.
Background technology
Formaldehyde is a kind of important Organic chemical products and important chemical intermediate, is widely used in medicine, dyestuff and engineering materials, if the polyformaldehyde resin taking formaldehyde as raw material is a kind of engineering plastics of high-quality, is widely used in electrical equipment, electronics and auto parts manufacture.Producing paraformaldehyde and polyformaldehyde resin needs high-concentration formaldehyde as raw material.But at present industrially produces formaldehyde by methanol catalytic oxidation, no matter adopt silver-colored method or iron molybdate catalyst method to produce, have a large amount of water generations.The concentration of producing all can not exceed 55%, all needs to remove a large amount of water while producing polyoxymethylene.Not only energy consumption is very large, and exists rare formaldehyde to recycle and the problem such as the corrosion of equipment.Because the vapour pressure of formalin is very low, formaldehyde and water can also form azeotrope simultaneously, and separation and purification anhydrous formaldehyde are very difficult and expensive.The technology of the methylal high-concentration formaldehyde processed of the Asahi Kasei Corporation of Japan and the exploitation of Bai Shide company of Sweden, it is the common method of preparing at present high-concentration formaldehyde, in addition, by methanol oxidation Oxidative Dehydrogenation anhydrous formaldehyde, it is a up-and-coming process, its product formaldehyde is easy to separate with hydrogen, and there will not be the problem of by product formic acid etching apparatus, but still in the laboratory study stage.
Dme is a derivative of methyl alcohol, and under the effect of an acidic catalyst, bimolecular methanol dehydration just generates the dme of a part.With respect to prepn. of formaldehyde by oxidation of methanol, in the product of dme oxidation formaldehyde processed, the content of water is the former half, and this is for taking high-concentration formaldehyde as raw material downstream application, and tool has very important significance.If again the water generating, further with the reaction that is hydrolyzed of raw material dme, make the formaldehyde of greater concn, the while can be improved transformation efficiency and the speed of reaction of dme.The principle of this process is that the hydrolysis methyl alcohol processed of the oxidation of dme formaldehyde processed and dme is coupled, and produces formaldehyde the coproduction methylal of high density.
Summary of the invention
The object of the present invention is to provide a kind of dme oxidation high-concentration formaldehyde processed, and the method for coproduction methylal.
For achieving the above object, method of the present invention comprises the unstripped gas that contains dme and oxygen by being loaded with the reactor of two-phase catalyzer, at pressure 0.1～0.5Mpa, the volume space velocity 1000～10000h of reaction of 250～400 DEG C of temperature of reaction, reaction
-1under, produce formaldehyde coproduction methylal; Wherein said two-phase catalyzer contains molybdenum and/or vanadium oxide catalyst I and solid acid catalyst II; In described unstripped gas, the molar content of dme is 3～25%, and the molar content of oxygen is 10.0～40.0%, and surplus is the rare gas element as carrier gas.
In the present invention, described molybdenum and/or vanadium oxide catalyst I can be catalyst-loaded, and carrier is for being selected from aluminum oxide, and zirconium white, on a kind of or any several mixture in titanium dioxide and silicon-dioxide.
In the present invention, in described molybdenum and/or vanadium oxide catalyst I, can contain auxiliary agent.Auxiliary agent is a kind of or any several mixture in chosen from Fe, cerium, cobalt, chromium, lanthanum, tin-oxide.
In one embodiment of the invention, unstripped gas can be the gas mixture of dme and air.
In the present invention, described diluent gas is rare gas element, and it is selected from nitrogen, a kind of or any several gas mixture in helium and argon gas.
In the present invention, described solid acid catalyst II is for being selected from ZSM-5, MOR, β, Y molecular sieve and γ-Al
2o
3in a kind of or any several mixture.
In one embodiment of the invention, described molybdenum and/or vanadium oxide catalyst I account for 10～90wt% of total catalyst weight, and solid acid catalyst II accounts for 10～90wt% of total catalyst weight.
In one embodiment of the invention, described molybdenum and/or vanadium oxide catalyst I can use the precipitator method, gel method or solid phase method preparation.
The invention provides a kind of method of dme oxidation high-concentration formaldehyde processed coproduction methylal.In present method products therefrom, compare with prepn. of formaldehyde by oxidation of methanol, the concentration of formaldehyde is greatly improved.
Embodiment
In embodiment, the transformation efficiency of dme, formaldehyde selectivity and methylal selectivity all the carbon mole number based on dme are calculated:
Dimethyl ether conversion rate=[(dme carbon mole number in unstripped gas)-(dme carbon mole number in product)] ÷ (dme carbon mole number in unstripped gas) × (100%)
Formaldehyde selectivity=(the carbon mole number of formaldehyde in product) ÷ [(dme carbon mole number in unstripped gas)-(dme carbon mole number in product)) × (100%)
Methylal selectivity=(the carbon mole number of methylal in product) ÷ [(dme carbon mole number in unstripped gas)-(dme carbon mole number in product)) × (100%)
Below by embodiment in detail the present invention is described in detail, but the present invention is not limited to these embodiment.
The preparation method of embodiment 1 catalyzer
1.1 co-precipitated catalyst preparation process
The preparation of catalyzer adopts coprecipitation method, and ammonia soln is as precipitation agent, the mixed aqueous solution of the metal-salt of iron, molybdenum salt and one or more auxiliary agents is added in the ammonia soln of 35 DEG C to mixing solutions vigorous stirring with certain speed.Controlling precipitation pH value is 9.0.The precipitation of gained is aging through 12h, 120 DEG C of dry, 330-400 DEG C roastings obtain roasting sample.
1.2 coprecipitation method Kaolinite Preparation of Catalyst 180Mo100Fe5La5VO (atomic ratio, taking the molar content of iron as 100) preparation process
By 8.08g Fe (NO
3)
39H
2o, 5.976g (NH
4)
2mo
4o
132H
2o, 0.433g La (NO
3)
26H
2o and 0.117g NH
4vO
3be dissolved in 300ml deionized water, with 250ml deionized water dilution 18.65g strong aqua.At room temperature vigorous stirring ammonia soln, then slowly adds metal mixed salts solution in ammonia soln, joining day 20min left and right.Regulate and precipitate pH value to 9.0 with ammonia soln, after continuing to stir 150min, will precipitate age overnight.Precipitate with deionized water washing is extremely neutral, centrifugation.Gained is deposited in dry 12h in 120 DEG C of baking ovens, and dry rear sample is placed in retort furnace, is warmed up to 350 DEG C with the temperature rise rate of 2 DEG C/min, and roasting 3h, obtains the sample after roasting.Catalyzer consists of 180Mo100Fe5La5VO.
1.3 gel method Kaolinite Preparation of Catalyst 150Mo100Fe3La2VO (atomic ratio, taking the molar content of iron as 100) process
By 6.73g Fe (NO
3)
39H
2o, 5.976g (NH
4)
2mo
4o
132H
2o, 0.26g La (NO
3)
26H
2o and 0.047g NH
4vO
3be dissolved in 300ml deionized water, be made into mixing solutions, in EDTA: the ratio that metal ion (mol ratio) is 1.0: 1.0 adds the ammonia soln of ethylenediamine tetraacetic acid (EDTA) (EDTA), magnetic agitation, 80 DEG C of circulator baths heating.Then in mixing solutions in citric acid: the ratio that metal ion (mol ratio) is 1.5: 1.0 adds appropriate aqueous citric acid solution, at this moment in mixed solution, may there is precipitation, utilize ammoniacal liquor or nitre acid for adjusting pH value to be about 6, precipitation can rapidly disappear, and forms clear solution.Along with continuous heating, magnetic agitation, in solution, moisture constantly evaporates, and finally forms gel.Gel is transferred in pottery circle ware and at the temperature of 120 DEG C, heat-treated and to obtain powder for the first time.By first powder roasting 2h at 450 DEG C, to the sample after roasting.Catalyzer consists of 180Mo100Fe5La5VO.
1.4 solid phase method Kaolinite Preparation of Catalyst 180Mo100Fe5La5VO (atomic ratio, taking the molar content of iron as 100) process
By 8.08g Fe (NO
3)
39H
2o, 5.976g (NH
4)
2mo
4o
132H
2o, 0.433g La (NO
3)
26H
2o and 0.117g NH
4vO
3mix, in ball mill, mix and mill, be then to dry 12h at the temperature of 120 DEG C, dry after sample be placed in retort furnace, be warmed up to 300 DEG C with the temperature rise rate of 2 DEG C/min, roasting 5h, obtains the sample after roasting.Catalyzer consists of 180Mo100Fe5La5VO.
Embodiment 2: evaluating catalyst method
By the mixture of 1.0ml 20-40 object catalyst I and catalyst I I, put into fixed-bed reactor flat-temperature zone.Before reaction, catalyzer is activated with air, air velocity 60ml/min, activation temperature is 350 DEG C, pressure 0.1MPa, soak time 2h.After activation finishes, regulate temperature controller to 320 DEG C, quality of regulation under meter air flow quantity is 108ml/min (normal conditions), dme 8ml/min.Product on-line analysis, every 20min samples once.From reactor outlet to gas-chromatography ten-way valve entrance, all pipelines and back pressure valve all carry out heating and thermal insulation.
Embodiment 3: product analysis method
Products obtained therefrom is analyzed with Agilent 7890A.Chromatogram is furnished with dual-detector FID and TCD, and has a ten-way valve, can make product enter respectively packed column and capillary column simultaneously.The Chemstation software processes of Agilent for data.
The concrete chromatographic condition of Agilent is as follows:
Chromatogram: Agilent 7890A
FID chromatographic column: HP-PONA 19091S-001,50m x 0.2mm (internal diameter), 0.5 μ m thickness carrier gas: helium, 2.5ml/min
Post case temperature: 35 DEG C keep 5min
35-150℃，5℃/min
150 DEG C keep 10min
Injection port: shunting (100: 1) temperature: 170 DEG C
250 DEG C of detector: FID
TCD chromatographic column: polar column, porapakN 2m x 2mm (internal diameter)
Carrier gas: helium, 20ml/min
Post case temperature: 35 DEG C keep 5min
35-150℃，5℃/min
150 DEG C keep 10min
Injection port: temperature: 170 DEG C
200 DEG C of detector: TCD
Embodiment 4:
On 50wt%180Mo100Fe5La5VO and 50%H beta catalyst, the impact of differential responses temperature on dme oxidation formaldehyde processed coproduction methylal.Reaction conditions: reaction pressure=0.1Mpa, volume space velocity=5000h
-1, dme/(dme+oxygen+carrier gas) mol ratio=3%, oxygen/(dme+oxygen+carrier gas)=10.0%, remains as carrier gas nitrogen.
The impact of table 1 temperature on reaction
| Temperature of reaction (DEG C) | DME transformation efficiency (%) | Formaldehyde selectivity (%) | Methylal % |
| 250 | 16.00 | 63.91 | 15.9 |
| 270 | 19.84 | 66.05 | 17.7 |
| 280 | 21.36 | 69.15 | 19.1 |
| 290 | 24.16 | 72.41 | 23.6 |
| 300 | 27.71 | 73.95 | 22.4 |
| 320 | 29.68 | 69.89 | 19.5 |
| 350 | 30.78 | 63.43 | 16.4 |
| 400 | 31.52 | 51.67 | 14.6 |
Comparative example 1:
On 100%180Mo100Fe5La5VO catalyzer, do not add solid acid catalyst H β.The impact of differential responses temperature on dme oxidation formaldehyde processed coproduction methylal.Reaction conditions: reaction pressure=0.1Mpa, volume space velocity=5000h
-1, dme/(dme+oxygen+carrier gas) mol ratio=3%, oxygen/(dme+oxygen+carrier gas)=10.0%, remains as carrier gas nitrogen.
The impact of table 2 temperature on reaction
| Temperature of reaction (DEG C) | DME transformation efficiency (%) | Formaldehyde selectivity (%) | Methylal % |
| 250 | 8.34 | 71.78 | 2.4 |
| 270 | 12.65 | 76.65 | 3.3 |
| 280 | 14.88 | 79.33 | 4.6 |
| 290 | 17.98 | 76.87 | 5.8 |
| 300 | 19.71 | 74.78 | 5.6 |
| 320 | 21.97 | 73.54 | 4.3 |
| 350 | 23.66 | 70.43 | 4.2 |
| 400 | 24.52 | 64.65 | 3.4 |
Embodiment 5:
On 75wt%250Mo100Fe5LaO and 25wt%HY catalyzer, the impact of different reaction pressures on dme oxidation formaldehyde processed coproduction methylal.Reaction conditions: temperature of reaction=320 DEG C, volume space velocity=5000h
-1, dme/(dme+oxygen+carrier gas)=25%, oxygen/(dme+oxygen+carrier gas)=40.0%, remains as carrier gas He.
The impact of table 3 pressure on reaction
| Reaction pressure (G, MPa) | DME transformation efficiency (%) | Formaldehyde selectivity (%) | Methylal % |
| 0.1 | 26.34 | 73.76 | 18.2 |
| 0.2 | 24.46 | 72.59 | 21.5 |
| 0.3 | 21.38 | 71.15 | 23.1 |
| 0.4 | 17.67 | 70.89 | 25.6 |
| 0.5 | 15.15 | 69.66 | 26.4 |
Embodiment 6:
On 90wt%130Mo100Fe5VO and 10wt%HMOR catalyzer, the impact of different volume space velocities on dme oxidation formaldehyde processed coproduction methylal.Reaction conditions is as follows: temperature of reaction=320 DEG C, and reaction pressure=0.1MPa, dme/(dme+oxygen+carrier gas)=10%, oxygen/(dme+oxygen+carrier gas)=25.0%, remains as carrier gas N2.
The impact of table 4 volume space velocity on reaction
| Volume space velocity (h -1) | DME transformation efficiency (%) | Formaldehyde selectivity (%) | Methylal % |
| 1000 | 28.77 | 71.28 | 24.92 |
| 3500 | 24.61 | 71.49 | 21.73 |
| 6000 | 21.98 | 75.47 | 19.14 |
| 10000 | 15.54 | 78.19 | 15.62 |
Embodiment 7:
The reaction result of the catalyzer that different methods makes.Reaction conditions is as follows: temperature of reaction=320 DEG C, reaction pressure=0.1MPa, volume space velocity=2500h
-1, dme/(dme+oxygen+carrier gas)=25%, oxygen/(dme+oxygen+carrier gas)=40.0%, remains as carrier gas Ar.Wherein, solid acid catalyst is HZSM-5, accounts for the 30wt% of total catalyst.
Table 5. sample number into spectrum and preparation condition and result
Embodiment 8:
The reaction result of various combination catalyzer.Reaction conditions is as follows: temperature of reaction=320 DEG C, reaction pressure=0.1MPa, volume space velocity 2500h
-1, dme/(dme+oxygen+carrier gas)=25%, oxygen/(dme+oxygen+carrier gas)=40.0%, remains as carrier gas N2.
The reaction result of the loaded formaldehyde catalyst of table 6. and different solid acid catalysts
Claims (9)
1. prepare the method for formaldehyde coproduction methylal for one kind, it is characterized in that, by the unstripped gas that contains dme and oxygen by being loaded with the reactor of two-phase catalyzer, 250～400 DEG C of temperature of reaction, reaction pressure 0.1～0.5Mpa, the volume space velocity 1000～10000h of reaction
-1under, produce formaldehyde coproduction methylal; Wherein said two-phase catalyzer contains molybdenum and/or vanadium oxide catalyst I and solid acid catalyst II; In described unstripped gas, the molar content of dme is 3～25%, and the molar content of oxygen is 10.0～40.0%, and surplus is the rare gas element as carrier gas.
2. method according to claim 1, is characterized in that, described molybdenum and/or vanadium oxide catalyst I are catalyst-loaded, and carrier is for being selected from aluminum oxide, and zirconium white, on a kind of or any several mixture in titanium dioxide and silicon-dioxide.
3. method according to claim 1 and 2, is characterized in that, contains the auxiliary agent that is selected from lower group in described molybdenum and/or vanadium oxide catalyst I: a kind of or any several mixture in iron, cerium, cobalt, chromium, lanthanum, tin-oxide.
4. method according to claim 1, is characterized in that, described unstripped gas is the gas mixture of dme and air.
5. method according to claim 1, is characterized in that, described diluent gas is for being selected from nitrogen, helium, a kind of in argon gas or arbitrarily several gas mixtures.
6. method according to claim 1, is characterized in that, described solid acid catalyst II is for being selected from ZSM-5, MOR, β, Y molecular sieve and γ-Al
2o
3in a kind of or any several mixture.
7. method according to claim 1, is characterized in that, described solid acid catalyst II accounts for 10～90wt% of total catalyst weight.
8. method according to claim 1, is characterized in that, described molybdenum and/or vanadium oxide catalyst I adopt the precipitator method, gel method or solid phase method preparation.
9. method according to claim 1, is characterized in that, described molybdenum and/or vanadium oxide catalyst I account for 10～90wt% of total catalyst weight.
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|---|---|---|---|
| CN201210571082.6A CN103896749B (en) | 2012-12-25 | 2012-12-25 | A kind of method preparing formaldehyde co-production dimethoxym ethane |
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|---|---|---|---|
| CN201210571082.6A CN103896749B (en) | 2012-12-25 | 2012-12-25 | A kind of method preparing formaldehyde co-production dimethoxym ethane |
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|---|---|
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| CN103896749B CN103896749B (en) | 2016-09-14 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105585484A (en) * | 2014-11-17 | 2016-05-18 | 中国科学院大连化学物理研究所 | Method of improving performance of methylal carbonylation reaction catalyst |
| CN107778149A (en) * | 2016-08-26 | 2018-03-09 | 张也贤 | The method for preparing polymethoxy dimethyl ether |
| CN113019388A (en) * | 2019-12-09 | 2021-06-25 | 中国科学院大连化学物理研究所 | Catalyst for preparing formaldehyde by oxidizing dimethyl ether, preparation and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6392102B1 (en) * | 1998-11-12 | 2002-05-21 | Bp Corporation North America Inc. | Preparation of polyoxymethylene dimethyl ethers by catalytic conversion of formaldehyde formed by oxidation of dimethyl ether |
| US20050154226A1 (en) * | 2004-01-08 | 2005-07-14 | The Regents Of The University Of California | Oxidation of methanol and/or dimethyl ether using supported molybdenum-containing heteropolyacid catalysts |
-
2012
- 2012-12-25 CN CN201210571082.6A patent/CN103896749B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6392102B1 (en) * | 1998-11-12 | 2002-05-21 | Bp Corporation North America Inc. | Preparation of polyoxymethylene dimethyl ethers by catalytic conversion of formaldehyde formed by oxidation of dimethyl ether |
| US20050154226A1 (en) * | 2004-01-08 | 2005-07-14 | The Regents Of The University Of California | Oxidation of methanol and/or dimethyl ether using supported molybdenum-containing heteropolyacid catalysts |
Non-Patent Citations (1)
| Title |
|---|
| 黄秀敏等: "负载型MoOx 和VOx 催化剂上二甲醚选择氧化制甲醛反应", 《催化学报》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105585484A (en) * | 2014-11-17 | 2016-05-18 | 中国科学院大连化学物理研究所 | Method of improving performance of methylal carbonylation reaction catalyst |
| CN105585484B (en) * | 2014-11-17 | 2017-12-05 | 中国科学院大连化学物理研究所 | A kind of method for improving dimethoxym ethane carbonylation reaction catalyst performance |
| CN107778149A (en) * | 2016-08-26 | 2018-03-09 | 张也贤 | The method for preparing polymethoxy dimethyl ether |
| CN113019388A (en) * | 2019-12-09 | 2021-06-25 | 中国科学院大连化学物理研究所 | Catalyst for preparing formaldehyde by oxidizing dimethyl ether, preparation and application thereof |
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|---|---|
| CN103896749B (en) | 2016-09-14 |
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