CN102992965A - Process for preparing methyl tertiary butyl ether - Google Patents
Process for preparing methyl tertiary butyl ether Download PDFInfo
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- CN102992965A CN102992965A CN2012105856531A CN201210585653A CN102992965A CN 102992965 A CN102992965 A CN 102992965A CN 2012105856531 A CN2012105856531 A CN 2012105856531A CN 201210585653 A CN201210585653 A CN 201210585653A CN 102992965 A CN102992965 A CN 102992965A
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- butyl ether
- tertiary butyl
- methyl tertiary
- niobium
- roasting
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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Abstract
The invention discloses a process for preparing methyl tertiary butyl ether. The process comprises the steps of immersing gamma-Al2O3 in a niobium oxalate solution, roasting a solid-phase material obtained after filtering, then dipping, drying and roasting the solid-phase material in a sulfuric acid solution, obtaining a niobium-containing solid acid catalyst, and filling a stainless steel fixed bed integral reactor full of the niobium-containing solid acid catalyst. A micro pump is used for pressing a mixed liquid of tertiary butanol and methyl alcohol in an evaporator for gasification, vapor enters the fixed bed integral reactor with a heat-insulating layer for catalytic reaction, and the methyl tertiary butyl ether can be obtained continuously after condensation of gaseous products. The selectivity of the methyl tertiary butyl ether obtained by the process is within a range of 81.6-82.3%, and the conversion rate of the tertiary butanol is within a range of 45.5-46.5%. Compared with the prior art, the process has the advantages that the niobium-containing solid acid catalyst is used for preparing the methyl tertiary butyl ether, the activity and the stability of the niobium-containing solid acid catalyst are higher than those of a resin catalyst, the niobium-containing solid acid catalyst can be recycled after regeneration, obtained products are stable in quality, good in selectivity, high in conversion rate and applicable to industrial production.
Description
Technical field
The present invention relates to a kind of preparation method of methyl tertiary butyl ether, particularly a kind ofly contain the method that the niobium solid acid catalyst prepares methyl tertiary butyl ether.
Background technology
Methyl tertiary butyl ether claims again 2-methoxyl group-2-methylpropane, English tert-butyl methylether by name, be called for short MTBE, it is a kind of important industrial chemicals, methyl tertiary butyl ether can be used as analyzes solvent, extraction agent, can prepare high-purity iso-butylene by cracking, also be used for the production of Methylacrylaldehyde and methacrylic acid.Because methyl tertiary butyl ether has water-soluble low, resistance to acid is strong, oxidation-resistance is strong, toxicity is low, volatility is low, safety and stability, the characteristics that solvating ability is strong, the alternative ether of methyl tertiary butyl ether, tetrahydrofuran (THF), aromatic hydrocarbon, methylene dichloride equal solvent use, and are the highest ether of present world's annual production, and continue over a period to come the main ingredient as clean gasoline.
In the prior art, the reported in literature that many preparation MTBE are arranged, the industrial production that routinizes MTBE carries out addition reaction production by iso-butylene and methyl alcohol and obtains in the presence of catalyzer, wherein employed catalyzer mainly is the sulfonate resin take styrene-divinylbenzene copolymer as matrix, with Amberlyst-15, D
72The use of macroreticular acidic Zeo-karb is the most extensive, and there is following shortcoming in these spherical copolymer resins in the preparation process of methyl tertiary butyl ether: temperature of reaction only limits to below 90 ℃, and the temperature rising can cause the resin catalyst inactivation; Because this reaction is strong exothermal reaction, strengthen reaction velocity afterreaction temperature and be difficult to be effectively controlled, limited the raising of throughput; Can not regenerate behind the employed resin catalyst inactivation, cause the catalyzer consumption large, cost is high, is unfavorable for environmental protection.
Summary of the invention
Problem to be solved by this invention is to provide a kind of preparation method of methyl tertiary butyl ether, utilization contains the niobium solid acid catalyst and prepares methyl tertiary butyl ether, the temperature of reaction rising causes the resin catalyst inactivation in the prior art to overcome, strong exothermal reaction causes temperature of reaction to be difficult to control, production efficiency is low, is difficult to the deficiency of regenerating behind the catalyst deactivation.
Technical conceive of the present invention is as follows:
With γ-Al
2O
3Soak in niobium oxalate solution, the solid formation that filtration obtains floods at sulphuric acid soln after placing the muffle furnace roasting, dry, roasting, obtains containing the niobium solid acid catalyst, and it is filled in the full stainless steel integral fixed-bed reactor.With micro pump the mixed solution of the trimethyl carbinol-methyl alcohol being pressed into vaporizer gasifies, vapour enters with carrying out catalyzed reaction in the integral fixed-bed reactor of thermal insulation layer, reacted gas-phase product can obtain the reaction product methyl tertiary butyl ether continuously through condenser condenses.
To achieve these goals, the present invention adopts following technical scheme:
A kind of preparation method of methyl tertiary butyl ether comprises the steps:
(1) with γ-Al
2O
3Add in the niobium oxalate solution and soak, filtration after the immersion is carried out first roasting with filtering the solid formation that obtains, and is cooled to room temperature again, then with after dipping, drying, the roasting in the cooled solid formation adding sulphuric acid soln, obtains containing the niobium solid acid catalyst.
The solvent of above-mentioned niobium oxalate solution and sulphuric acid soln is water.
(2) the niobium solid acid catalyst that contains that step (1) is obtained is filled the stainless steel integral fixed-bed reactor that filled band has thermal insulation layer, the mixed solution of the trimethyl carbinol and methyl alcohol is gasified, vapour enters with carrying out catalyzed reaction in the integral fixed-bed reactor of thermal insulation layer, reacted gas-phase product can obtain methyl tertiary butyl ether continuously after condenser condenses, non-condensable gases is emptying behind deep cooling.
Preferably, in the step (1), described niobium oxalate is (NH
4)
3[NbO (C
2O
4)].
Preferably, in the step (1), the weight percent concentration of described niobium oxalate solution mesoxalic acid niobium is 6-8wt%; γ-Al
2O
3Quality and the volume ratio of niobium oxalate solution be 1: 8-10, g/ml.
Preferably, in the step (1), γ-Al
2O
3The condition of soaking in niobium oxalate solution is to soak 8-10 hour under the normal temperature.
Preferably, in the step (1), the condition that the solid formation that filter to obtain carries out roasting is for 900-950 ℃ roasting temperature 2-3 hour.More excellent, the solid formation that described filtration obtains places muffle furnace to carry out roasting.
Preferably, in the step (1), the concentration of sulfuric acid is 1.5-1.8mol/l in the described sulphuric acid soln; γ-Al
2O
3Quality and the volume ratio of sulphuric acid soln be 1: 1.0-1.2, g/ml.
Preferably, in the step (1), the time that described cooled solid formation floods in sulphuric acid soln is 4-5 hour.
Preferably, in the step (1), dry condition is under 110-120 ℃ the temperature dry 1-2 hour behind the dipping.More excellent, the solid formation after will flooding first before the described drying dries naturally.More excellent, adopt muffle furnace to carry out drying when dry.
Preferably, in the step (1), the condition that dried solid formation carries out roasting is for 500-550 ℃ roasting temperature 4-5 hour.More excellent, adopt muffle furnace to carry out roasting during dried solid formation roasting.
Preferably, in the step (2), the mol ratio of the trimethyl carbinol and methyl alcohol is 1 in the described trimethyl carbinol and the methyl alcohol mixed liquor: 2.5-3.5.
Stainless steel integral fixed-bed reactor of the present invention can adopt existing integral fixed-bed reactor in the prior art, and this integral fixed-bed reactor need to be with thermal insulation layer, and its vapour carries out catalyzed reaction in the integral fixed-bed reactor of thermal insulation layer.The present invention is preferably the stainless steel integral fixed-bed reactor that specification is D32mm * 2mm * 600mm.
Preferably, in the step (2), when the mixed solution of the trimethyl carbinol and methyl alcohol is gasified, adopt micro pump that the mixed solution of the trimethyl carbinol and methyl alcohol is pressed into vaporizer with the air speed of 0.9-1.0ml/g.h and gasify.
Preferably, in the step (2), the holding temperature of described thermal insulation layer is 110-120 ℃.
The present invention uses contains the niobium solid acid catalyst and uses behind the inactivation more successively by recovering catalytic activity after the steps such as roasting, sulfuric acid dipping, drying, roasting, reusable.The condition of this successively roasting, sulfuric acid dipping, drying, roasting and the above-mentioned term harmonization that contains the preparation of niobium solid acid catalyst.
The selectivity of the methyl tertiary butyl ether that the preparation method of employing methyl tertiary butyl ether of the present invention obtains is 81.6-82.3%, and the transformation efficiency of the trimethyl carbinol is 45.5-46.5%.
The present invention compared with prior art, its beneficial effect is as follows:
The present invention's employing contains the niobium solid acid catalyst and prepares methyl tertiary butyl ether, and its active and stable styrene-divinylbenzene copolymer that is higher than the prior art employing is the sulfonate resin of matrix, such as Amberlyst-15, D
72The macroreticular acidic Zeo-karb, can be recycled after the niobium solid acid catalyst is regenerated of the present invention containing, the constant product quality that obtains, selectivity is good, is suitable for suitability for industrialized production.
Embodiment
The present invention is described further below by specific embodiment, but embodiment does not limit protection scope of the present invention.
Embodiment 1
With 100g γ-Al
2O
3Add in the 1000ml 6wt% niobium oxalate solution, soaked 10 hours under the normal temperature, the solid formation that filtration obtains places muffle furnace, roasting is 2 hours under 900 ℃ condition, is cooled to room temperature and is placed in the porcelain crucible, and the sulfuric acid that adds 100ml 1.8mol/l flooded 4 hours, naturally dry and be placed in the muffle furnace, under 110 ℃ temperature dry 2 hours, 500 ℃ roasting temperatures 5 hours, make and contain niobium solid acid catalyst 118g.
Contain the niobium solid acid catalyst to fill full specification be in the stainless steel integral fixed-bed reactor of D32mm * 2mm * 600mm with thermal insulation layer above-mentioned, with the mixed solution (trimethyl carbinol: methyl alcohol=1: 3 of micro pump with the trimethyl carbinol and methyl alcohol, mol ratio) being pressed into vaporizer with the air speed of 0.9ml/g.h gasifies, vapour is by the integral fixed-bed reactor with thermal insulation layer, under 110 ℃ condition, carry out catalyzed reaction, reacted gas-phase product is through condenser condenses, obtain continuously methyl tertiary butyl ether, non-condensable gases is emptying behind deep cooling.By analysis, the selectivity of methyl tertiary butyl ether is 82.3%, and the transformation efficiency of the trimethyl carbinol is 46.5%.
The methyl tertiary butyl ether that obtains is carried out analyzing and testing, its purity 〉=99.5%, detected result is as follows:
| Test item | Standard value | Measured value |
| Content | ≥99.0％ | 99.86％ |
| Refractive index | 1.366-1.370 | 1.369 |
| The trimethyl carbinol and methyl alcohol total amount | ≤0.5％ | Do not detect |
| Other total impurities | ≤1.0％ | 0.02％ |
| Moisture | ≤0.10％ | 0.10％ |
| Residue on evaporation | ≤0.02％ | 0.02％ |
Embodiment 2
With 100g γ-Al
2O
3In 800ml 8wt% niobium oxalate solution, soaked 8 hours under the normal temperature, the solid formation that filtration obtains places muffle furnace, roasting is 3 hours under 950 ℃ condition, is cooled to room temperature and is placed in the porcelain crucible, and the sulfuric acid that adds 120ml 1.5mol/l flooded 5 hours, naturally dry and be placed in the muffle furnace, under 120 ℃ temperature dry 1 hour, 550 ℃ roasting temperatures 4 hours, make and contain niobium solid acid catalyst 117g.
Contain the niobium solid acid catalyst to fill full specification be in the stainless steel integral fixed-bed reactor of D32mm * 2mm * 600mm with thermal insulation layer above-mentioned, with the mixed solution (trimethyl carbinol: methyl alcohol=1: 3 of micro pump with the trimethyl carbinol and methyl alcohol, mol ratio) being pressed into vaporizer with the air speed of 1.0ml/g.h gasifies, vapour is by the integral fixed-bed reactor with thermal insulation layer, under 120 ℃ condition, carry out catalyzed reaction, reacted gas-phase product is through condenser condenses, obtain continuously methyl tertiary butyl ether, non-condensable gases is emptying behind deep cooling.By analysis, the selectivity of methyl tertiary butyl ether is 81.6%, and the transformation efficiency of the trimethyl carbinol is 45.5%.
The methyl tertiary butyl ether that obtains is carried out analyzing and testing, its purity 〉=99.5%.
Embodiment 3
With 100g γ-Al
2O
3In 900ml 7wt% niobium oxalate solution, soaked 9 hours under the normal temperature, the solid formation that filtration obtains places muffle furnace, roasting is 2.5 hours under 950 ℃ condition, is cooled to room temperature and is placed in the porcelain crucible, and the sulfuric acid that adds 115ml 1.7mol/l flooded 4.5 hours, naturally dry and be placed in the muffle furnace, under 120 ℃ temperature dry 1.5 hours, 550 ℃ roasting temperatures 4.5 hours, make and contain niobium solid acid catalyst 117.5g.
Contain the niobium solid acid catalyst to fill full specification be in the stainless steel integral fixed-bed reactor of D32mm * 2mm * 600mm with thermal insulation layer above-mentioned, with the mixed solution (trimethyl carbinol: methyl alcohol=1: 2.5 of micro pump with the trimethyl carbinol-methyl alcohol, mol ratio) being pressed into vaporizer with the air speed of 0.95ml/g.h gasifies, vapour is by the integral fixed-bed reactor with thermal insulation layer, under 115 ℃ condition, carry out catalyzed reaction, reacted gas-phase product is through condenser condenses, obtain continuously methyl tertiary butyl ether, non-condensable gases is emptying behind deep cooling.By analysis, the selectivity of methyl tertiary butyl ether is 82.0%, and the transformation efficiency of the trimethyl carbinol is 46.0%.
The methyl tertiary butyl ether that obtains is carried out analyzing and testing, its purity 〉=99.5%.
Embodiment 4
With 100g γ-Al
2O
3In 900ml 7wt% niobium oxalate solution, soaked 9 hours under the normal temperature, the solid formation that filtration obtains places muffle furnace, roasting is 2.5 hours under 950 ℃ condition, is cooled to room temperature and is placed in the porcelain crucible, and the sulfuric acid that adds 115ml 1.7mol/l flooded 4.5 hours, naturally dry and be placed in the muffle furnace, under 120 ℃ temperature dry 1.5 hours, 500 ℃ roasting temperatures 5 hours, make and contain niobium solid acid catalyst 117.5g.
Contain the niobium solid acid catalyst to be full of specification be in the stainless steel integral fixed-bed reactor of D32mm * 2mm * 600mm with thermal insulation layer above-mentioned, with the mixed solution (trimethyl carbinol: methyl alcohol=1: 3.5 of micro pump with the trimethyl carbinol-methyl alcohol, mol ratio) being pressed into vaporizer with the air speed of 1.0ml/g.h gasifies, vapour enters the integral fixed-bed reactor with thermal insulation layer, under 115 ℃ condition, carry out catalyzed reaction, reacted gas-phase product is through condenser condenses, obtain continuously methyl tertiary butyl ether, non-condensable gases is emptying behind deep cooling.By analysis, the selectivity of methyl tertiary butyl ether is 82.1%, and the transformation efficiency of the trimethyl carbinol is 46.2%.
The methyl tertiary butyl ether that obtains is carried out analyzing and testing, its purity 〉=99.5%.
Need to prove that above embodiment is only unrestricted in order to technical scheme of the present invention to be described.Although with reference to preferred embodiment the present invention is had been described in detail, those of ordinary skill in the art is to be understood that, can make amendment or be equal to replacement the technical scheme of invention, and not break away from the scope of technical solution of the present invention, it all should be encompassed in the claim scope of the present invention.
Claims (10)
1. the preparation method of a methyl tertiary butyl ether comprises the steps:
(1) with γ-Al
2O
3Add in the niobium oxalate solution and soak, filtration after the immersion is carried out first roasting with filtering the solid formation that obtains, and is cooled to room temperature again, then with after dipping, drying, the roasting in the cooled solid formation adding sulphuric acid soln, obtains containing the niobium solid acid catalyst;
(2) the niobium solid acid catalyst that contains that step (1) is obtained is filled the integral fixed-bed reactor that filled band has thermal insulation layer, the mixed solution of the trimethyl carbinol and methyl alcohol is gasified, vapour enters with carrying out catalyzed reaction in the integral fixed-bed reactor of thermal insulation layer, can obtain continuously described methyl tertiary butyl ether after the reacted gas-phase product condensation, non-condensable gases is emptying behind deep cooling.
2. the preparation method of methyl tertiary butyl ether as claimed in claim 1 is characterized in that, in the step (1), described niobium oxalate is (NH
4)
3[NbO (C
2O
4)].
3. the preparation method of methyl tertiary butyl ether as claimed in claim 1 is characterized in that, in the step (1), the weight percent concentration of described niobium oxalate solution mesoxalic acid niobium is 6-8wt%; Described γ-Al
2O
3Quality and the volume ratio of described niobium oxalate solution be 1: 8-10.
4. the preparation method of methyl tertiary butyl ether as claimed in claim 1 is characterized in that, in the step (1), the concentration of sulfuric acid is 1.5-1.8mol/l in the described sulphuric acid soln; Described γ-Al
2O
3Quality and the volume ratio of described sulphuric acid soln be 1: 1.0-1.2.
5. the preparation method of methyl tertiary butyl ether as claimed in claim 1 is characterized in that,
In the step (1), the condition that the solid formation that filter to obtain carries out roasting is for 900-950 ℃ roasting temperature 2-3 hour;
In the step (1), the condition that dried solid formation carries out roasting is for 500-550 ℃ roasting temperature 4-5 hour.
6. the preparation method of methyl tertiary butyl ether as claimed in claim 1 is characterized in that,
In the step (1), γ-Al
2O
3The condition of soaking in niobium oxalate solution is to soak 8-10 hour under the normal temperature;
In the step (1), the time that described cooled solid formation floods in sulphuric acid soln is 4-5 hour;
In the step (1), dry condition is under 110-120 ℃ the temperature dry 1-2 hour behind the dipping.
7. the preparation method of methyl tertiary butyl ether as claimed in claim 1 is characterized in that, in the step (2), the mol ratio of the trimethyl carbinol and methyl alcohol is 1 in the described trimethyl carbinol and the methyl alcohol mixed liquor: 2.5-3.5.
8. the preparation method of methyl tertiary butyl ether as claimed in claim 1 is characterized in that,
In the step (2), described integral fixed-bed reactor is the stainless steel integral fixed-bed reactor of specification D32mm * 2mm * 600mm;
In the step (2), when the mixed solution of the trimethyl carbinol and methyl alcohol is gasified, adopt micro pump that the mixed solution of the trimethyl carbinol and methyl alcohol is pressed into vaporizer with the air speed of 0.9-1.0ml/g.h and gasify.
9. the preparation method of methyl tertiary butyl ether as claimed in claim 1 is characterized in that, in the step (2), the holding temperature of described thermal insulation layer is 110-120 ℃.
10. such as the preparation method of the arbitrary described methyl tertiary butyl ether of claim 1-9, it is characterized in that, described contain the niobium solid acid catalyst after using inactivation more successively by recovering catalytic activity behind roasting, sulphuric acid soln dipping, dry, the calcination steps.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105622361A (en) * | 2014-11-06 | 2016-06-01 | 苏州华一新能源科技有限公司 | Methyl tert-butyl ether synthesis method |
| CN106040265A (en) * | 2016-06-13 | 2016-10-26 | 孟红琳 | Method for preparing catalyst for synthesizing methyl tert-butyl ether |
| CN106083535A (en) * | 2016-06-13 | 2016-11-09 | 孟红琳 | A kind of preparation method of the methyl tertiary butyl ether(MTBE) of high conversion |
| CN108558612A (en) * | 2018-04-25 | 2018-09-21 | 陈久仓 | A kind of preparation method of methyl tertiary butyl ether(MTBE) |
Citations (1)
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| CN101147860A (en) * | 2006-09-20 | 2008-03-26 | 中国石油化工股份有限公司 | Catalyst for preparing dimethyl ether from methanol |
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2012
- 2012-12-28 CN CN201210585653.1A patent/CN102992965B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101147860A (en) * | 2006-09-20 | 2008-03-26 | 中国石油化工股份有限公司 | Catalyst for preparing dimethyl ether from methanol |
Non-Patent Citations (1)
| Title |
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| JOHN F. KNIFTON ET AL.: "Methyl tert-butyl ether synthesis from tert-butanol via inorganic solid acid catalysis", 《APPLIED CATALYSIS A: GENERAL》, vol. 183, 31 December 1999 (1999-12-31), pages 1 - 13 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105622361A (en) * | 2014-11-06 | 2016-06-01 | 苏州华一新能源科技有限公司 | Methyl tert-butyl ether synthesis method |
| CN106040265A (en) * | 2016-06-13 | 2016-10-26 | 孟红琳 | Method for preparing catalyst for synthesizing methyl tert-butyl ether |
| CN106083535A (en) * | 2016-06-13 | 2016-11-09 | 孟红琳 | A kind of preparation method of the methyl tertiary butyl ether(MTBE) of high conversion |
| CN108558612A (en) * | 2018-04-25 | 2018-09-21 | 陈久仓 | A kind of preparation method of methyl tertiary butyl ether(MTBE) |
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