CN1160601A - Methyl formate catalyst prepared through methanol carboxylation and its preparation process - Google Patents
Methyl formate catalyst prepared through methanol carboxylation and its preparation process Download PDFInfo
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- CN1160601A CN1160601A CN 96103148 CN96103148A CN1160601A CN 1160601 A CN1160601 A CN 1160601A CN 96103148 CN96103148 CN 96103148 CN 96103148 A CN96103148 A CN 96103148A CN 1160601 A CN1160601 A CN 1160601A
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Abstract
The catalyst is prepared with alcoholate of alkali metal, by using molecular sieve SO2 or Al2O3 as carrier and methanol or its mixture with polyglycol as liquid film phase solvent, and through soaking and vacuum drying, with the amount of loaded alcoholate of alkali metal being 10-70 wt% of carrier and the amount of liquid film phase solvent being less than carrier pore volume. The catalyst is used in low-pressure non-uniform catalytic methanol carboxylation to prepare methyl formate with a methyl formate selectivity of 100% and a yield of 1.9 g each hour and each gram of catalyst.
Description
The present invention relates to a kind of technological development field of heterogeneous catalysis methyl alcohol carbonylation system methyl formate.
Since nineteen twenty-five is delivered relevant first patent of methyl alcohol liquid phase catalytic carbonylation system methyl formate [Brit.Pat.252848 (1925) to BASF], the high pressure methyl alcohol liquid phase carbonylation of alkali alcoholate catalysis is the main path of industrial production methyl formate always, this is reflected at 333～363k, carries out under the condition of 3.0～8.0MPa.Yet this liquid-like phase homogeneous catalysis system exists the separation problem of catalyst with product inevitably: intermittently reactive mode in batches makes catalyst must separate trivial operations after a wheel operation.1978, Donald Lee Smathen[U.S.Pat.4 100 360 (1978)] once reported a kind of anion highly basic exchange resin catalyst that can be used for heterogeneous system, but because of its activity is too low, and do not have practical value.
Purpose of the present invention is intended to develop a kind of support type highly basic liquid film methyl alcohol carbonylation effective catalyst, at fixed bed gas continuous flow reactor, realizes heterogeneous catalysis methyl alcohol carbonylation system methyl formate, to substitute existing methyl alcohol liquid phase catalytic carbonylation technology.
The said catalyst of the present invention is by alkali alcoholate, and liquid film phase solvent and carrier are formed, and said alkali alcoholate is Li, Na, K, the methylate of Cs; The liquid film phase solvent is the mixture of methyl alcohol or methyl alcohol and polyethylene glycol (PEG); Carrier is molecular sieve or SiO
2Or Al
2O
3, molecular sieve can be selected from the A type, X type, Y type, M type or ZSM-5 type, particularly A4 type, 13X type, NaY type, NaM type or NaZSM-5 type.The load capacity of alkali alcoholate (in alkali metal) is (10.0%～70.0) Wt% of vehicle weight, preferably (15.0～50.0) Wt%, especially (20～40) Wt%.PEG amount in methyl alcohol and the PEG mixture liquid film phase solvent is (0.1～30.0) Wt% of carrier amount, preferably (0.1～20.0) Wt%.The liquid film dosage (volume) that mixes exceeds to be no more than pore volume at most.
Catalyst adopts conventional immersion process for preparing.The pretreated carrier of 40～60 orders with metering, after the reduced pressure treatment of finding time, the alkali metal methylate and the liquid film phase solvent that add metering, at room temperature flooded 3～8 hours, be placed on 353K water-bath heating, the drying under reduced pressure of finding time, (vacuum-10～-wide range of 600mmHg in), remove excessive CH
3OH promptly obtains the support type aqueous alkali film catalyst sample that will prepare.
The alkali metal carbinol compound prepares according to a conventional method.Promptly directly react and make with methyl alcohol by alkali metal.
Several carriers are before the dipping active component, preferably through following preliminary treatment:
NaY, NaZSM-5 type molecular sieve were prior to 673K calcination 2～5 hours, and the back compressing tablet is cooled off in dehydration, and is broken again, sieves out 40～60 order granularities.
13X, 4A type molecular sieve are earlier with NaOH liquid dipping, after washing is dried under 393K, the back compressing tablet is cooled off in 673K calcination 2～5 hours, and is broken again, sieves out 40～60 order granularities.
SiO
2Adopt 40～60 order granularities, earlier with NaOH liquid dipping, after 673K calcination 2～5 hours is dried in washing under 393K.
γ-Al
2O
3Adopt 40～60 order granularities, 673K calcination 2～5 hours.
Evaluating catalyst carries out in fixed bed gas continuous-flow reaction system, reactor feed gas CO imports methanol evaporator after purifying, bubbling and mistake, the methanol steam content of being taken away can just be regulated and control by the heating tape temperature that is wrapped in bubbling evaporimeter outside.Heterogeneous catalysis methyl alcohol carbonylation is 353～373K in temperature, and pressure is to carry out under the reaction condition of 0.4～3.0MPa.The composition of reaction gas and product is by an on-line gas chromatography analysis.Evaluation experimental is the result show.At 353K, 1.0MPa, CO/CH
3OH=6.5 (mol ratio), reaction gas flow velocity are under the reaction condition of 11160mL (STP)/h-mL catalyst, at KOCH
3-CH
3On the OH/NaY catalyst, methanol conversion X
CH3OHCan reach 29%, methyl formate (MF) selectivity S
MFReach 100%, the space-time yield Y of methyl formate
MFReach as high as the level of 1.9 Grams Per Hours-Ke catalyst.
The invention provides a kind of activity and selectivity height, the prepared through methanol carboxylation methyl formate effective catalyst that operational stability is good, this catalyst is simple for production, good reproducibility.It is innovation to existing high pressure liquid phase catalysis methanol carbonylation system methyl formate technology.Both overcome the step shortcoming of high pressure liquid phase catalytic carbonylation process operation, and the separating treatment operation that can exempt numerous and diverse catalyst and product, its comprehensive technical indexes reaches the requirement of industrialized developing.
The invention will be further described by embodiment below.
Embodiment 1
Take by weighing 1.0 grams, 40～60 orders through 5 hours NaY type molecular sieve of 673K calcination, the drying under reduced pressure 5 minutes of under normal temperature, finding time, the back adds 4.0 milligrams of 2M KOCH
3-CH
3OH solution, dipping spends the night, and the back reduction vaporization drying of finding time under 323K has good fluidity until the sample particle, promptly is transferred to the stainless steel reactor of 8 * 1.5 millimeters of φ, at 1.0MPa, 353K, unstripped gas is formed CO/CH
3OH=6.5 (mol ratio), unstripped gas air speed GHSV=1.1X10
4Hour
-1Reaction condition under catalyst is estimated; The result shows that reaction reaches stable state very soon, and in the test that lasts 6 hours, the space-time yield of methyl formate stably reaches 1.9 Grams Per Hours-Ke catalyst; The selectivity of product methyl formate is 100%.
Embodiment 2
Take by weighing 1.0 grams, 40～60 orders through 5 hours NaZSSM-5 type (Si/Al=18) molecular sieve of 673K calcination, the drying under reduced pressure 5 minutes of under normal temperature, finding time, 3.0 milliliters of 2M KOCH are injected in the back
3-CH
3OH solution, dipping spends the night, and the back reduction vaporization drying of finding time under 323K has good fluidity until the sample particle, promptly is transferred to the stainless steel reactor of 8 * 1.5 millimeters of φ, at 2.0MPa, 353K, unstripped gas is formed CO/CH
3OH=9.3 (mol ratio), unstripped gas air speed GHSV=1500 hour
-1Reaction condition under catalyst is estimated; The result shows that reaction reaches stable state very soon, and in the test that lasts 6 hours, the space-time yield of methyl formate stably reaches 270 milligrams/hour-Ke catalyst; The selectivity of product methyl formate is 100%.
Embodiment 3
Take by weighing 1.0 grams, 40～60 orders through 5 hours NaZSM-5 type (Si/Al=18) molecular sieve of 673K calcination, the drying under reduced pressure 5 minutes of under normal temperature, finding time, 3.0 milliliters of 2M KOCH are injected in the back
3-CH
3OH solution and 0.2 milliliter of PEG (M=400), dipping spends the night, and the back reduction vaporization drying of finding time under 323K has good fluidity until the sample particle, promptly is transferred to the stainless steel reactor of 8 * 1.5 millimeters of φ, at 1.0MPa, 353K, unstripped gas is formed CO/CH
3OH=1.1 (mol ratio), unstripped gas air speed GHSV=1500 hour
-1Reaction condition under catalyst is estimated; The result shows that reaction reaches stable state very soon, and in the test that lasts 6 hours, the space-time yield of methyl formate stably reaches 715 milligrams/hour-Ke catalyst; The selectivity of product methyl formate is 100%.
Embodiment 4
With a certain amount of 40～60 order 13X type molecular sieves, spend the night through appropriate amount 1M NaOH solution impregnation, after washing, the 393K oven dry 673K calcination 5 hours, is cooled off standby.
It is above-mentioned through pretreated 13X molecular sieve sample to take by weighing 1.0 grams, the drying under reduced pressure 5 minutes of finding time at normal temperatures, and the back adds 3.0 milliliters of 2M KOCH
3-CH
3OH solution and 0.1 milliliter of PEG (M=400), dipping spends the night, and the back reduction vaporization drying of finding time under 323K has good fluidity until the sample particle, promptly is transferred to the stainless steel reactor of 8 * 1.5 millimeters of φ, at 1.0MPa, 353K, unstripped gas is formed CO/CH
3OH=1.1 (mol ratio), gaseous hourly space velocity GHSV=1500 hour
-1Reaction condition under catalyst is estimated; The result shows that reaction reaches stable state very soon, and in the test that lasts 6 hours, the space-time yield of methyl formate stably reaches 660 milligrams/hour-Ke catalyst; The selectivity of product methyl formate reaches 100%.
Embodiment 5
With a certain amount of 40～60 order 4A type molecular sieves, spend the night through appropriate amount 1M NaOH solution impregnation, after washing, the 393K oven dry 673K calcination 5 hours, is cooled off standby.
It is above-mentioned through pretreated 4A molecular sieve sample to take by weighing 1.0 grams, the drying under reduced pressure 5 minutes of finding time at normal temperatures, and the back adds 3.0 milliliters of 2M KOCH
3-C
3OH solution and 0.05 milliliter of PEG (M=400), dipping spends the night, and the back reduction vaporization drying of finding time under 323K has good fluidity until the sample particle, promptly is transferred to the stainless steel reactor of 8 * 1.8 millimeters of φ, at 1.0MPa, 353K, unstripped gas is formed CO/CH
3OH=1.1 (mol ratio), gaseous hourly space velocity GHSV=1500 hour
-1Reaction condition under catalyst is estimated; The result shows that reaction reaches stable state very soon, and in the test that lasts 6 hours, the space-time yield of methyl formate stably reaches 710 milligrams/hour-Ke catalyst, and the selectivity of product methyl formate reaches 100%.
Embodiment 6
Take by weighing 1.0 grams, 40～60 orders through 5 hours NaY type molecular sieve of 673K calcination, the drying under reduced pressure 5 minutes of under normal temperature, finding time, the back adds 3.0 milliliters of 2M NaOCH
3-CH
3OH solution, dipping spends the night, and the back reduction vaporization drying of finding time under 323K has good fluidity until the sample particle, promptly is transferred to the stainless steel reactor of 8 * 1.5 millimeters of φ, at 2.0MPa, 353K, unstripped gas is formed CO/CH
3OH=8.5, gaseous hourly space velocity GHSV=1500 hour
-1Reaction condition under catalyst is estimated; The result shows that reaction reaches stable state very soon, in the test that lasts 6 hours, and stable 240 milligrams/hour-Ke catalyst that reaches of the space-time yield of methyl formate; The selectivity of product methyl formate reaches 100%.
Embodiment 7
Get a certain amount of 40～60 order silica gel (SiO
2), spend the night through appropriate amount 1M NaOH solution impregnation, after washing, the 393K oven dry 673K calcination 5 hours, is cooled off standby.
It is above-mentioned through pretreated silica gel (SiO to take by weighing 1.0 grams
2) sample, the drying under reduced pressure 5 minutes of finding time at normal temperatures, the back adds 3.0 milliliters of 2M KOCH
3-CH
3OH solution and 0.2 milliliter of PEG (M=600), dipping spends the night, and the back reduction vaporization drying of finding time under 323K has good fluidity until the sample particle, promptly is transferred to the stainless steel reactor of 8 * 1.5 millimeters of φ, at 2.0MPa, 353K, unstripped gas is formed CO/CH
3OH=2.0 (mol ratio), unstripped gas air speed GHSV=1500 hour
-1Reaction condition under catalyst is estimated; The result shows that reaction reaches stable state very soon, and the space-time yield of 2 hours methyl formates of reaction stably reaches 540 milligrams/hour-Ke catalyst; The selectivity of product methyl formate is 100%.
Embodiment 8
Take by weighing 1.0 grams, 40～60 orders through γ-Al of 5 hours of 673K calcination
2O
3Sample, the drying under reduced pressure 5 minutes of finding time at normal temperatures, the back adds 3.0 milliliters of 2M KOCH
3-CH
3OH solution and 0.2 milliliter of PEG (M=400), dipping spends the night, and the back reduction vaporization drying of finding time under 323K has good fluidity until sample, promptly is transferred to the stainless steel reactor of 8 * 1.5 millimeters of φ, at 2.0MPa, 353K, unstripped gas is formed CO/CH
3OH=5.5 (mol ratio), gaseous hourly space velocity GHSV=1500 hour
-1Reaction condition under catalyst is estimated; The result shows that reaction reaches stable state very soon, and the space-time yield of 4 hours methyl formates of reaction stably reaches 230 milligrams/hour-Ke catalyst; The selectivity of product methyl formate is 100%.
Claims (8)
1. prepared through methanol carboxylation methyl formate catalyst, the alkali metal containing alcoholates, it is characterized in that also containing a kind of carrier and liquid film phase solvent, said alkali alcoholate is Li, Na, K, the methylate of Cs, the liquid film phase solvent is the mixture of methyl alcohol or methyl alcohol and polyethylene glycol (PEG), and carrier is molecular sieve or SiO
2Or Al
2O
3The load capacity of alkali alcoholate (in alkali metal) is (10.0～70.0) wt% of vehicle weight, liquid film dosage (the volume)≤pore volume that mixes.
2. prepared through methanol carboxylation methyl formate catalyst as claimed in claim 1 is characterized in that molecular sieve is the A type, X type, Y type, M type or ZSM-5 type.
3. prepared through methanol carboxylation methyl formate catalyst as claimed in claim 2 is characterized in that molecular sieve is the A4 type, 13X type, NaY type, NaM or NaZSM-5 type.
4. prepared through methanol carboxylation methyl formate catalyst as claimed in claim 1, the load capacity (in alkali metal) that it is characterized in that alkali alcoholate are (15.0～50.0) wt% of vehicle weight.
5. prepared through methanol carboxylation methyl formate catalyst as claimed in claim 4, the load capacity (in alkali metal) that it is characterized in that alkali alcoholate are (20～40) wt% of vehicle weight.
6. prepared through methanol carboxylation methyl formate catalyst as claimed in claim 1 is characterized in that the PEG amount in methyl alcohol and the PEG mixture liquid film phase solvent is (0.1～20.0) wt% of carrier amount.
7. prepared through methanol carboxylation methyl formate Preparation of catalysts method, it is characterized in that the pretreated carrier of 40～60 orders with metering, after the decompression of finding time under the normal temperature, the alkali alcoholate and the liquid film phase solvent that add metering, at room temperature flooded 3～8 hours, place 353K water-bath heating then, the drying under reduced pressure of finding time (vacuum-10～-600mmHg).
8. prepared through methanol carboxylation methyl formate Preparation of catalysts method as claimed in claim 7 is characterized in that carrier is before the dipping active constituent, through following preliminary treatment:
NaY, NaZSM-5 type molecular sieve were prior to 673K calcination 2～5 hours, and the back compressing tablet is cooled off in dehydration, and is broken again, sieves out 40～60 order granularities;
13X, 4A type molecular sieve are earlier with NaOH liquid dipping, after washing is dried under 393K, the back compressing tablet is cooled off in 673K calcination 2～5 hours, and is broken again, sieves out 40～60 order granularities;
SiO
2Adopt 40～60 order granularities, earlier with NaOH liquid dipping, after 673K calcination 2～5 hours is dried in washing under 393K;
γ-Al
2O
3Adopt 40～60 order granularities, 673K calcination 2～5 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96103148A CN1048656C (en) | 1996-03-21 | 1996-03-21 | Methyl formate catalyst prepared through methanol carboxylation and its preparation process |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96103148A CN1048656C (en) | 1996-03-21 | 1996-03-21 | Methyl formate catalyst prepared through methanol carboxylation and its preparation process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1160601A true CN1160601A (en) | 1997-10-01 |
| CN1048656C CN1048656C (en) | 2000-01-26 |
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ID=5117892
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96103148A Expired - Fee Related CN1048656C (en) | 1996-03-21 | 1996-03-21 | Methyl formate catalyst prepared through methanol carboxylation and its preparation process |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1085108C (en) * | 1998-06-10 | 2002-05-22 | 中国科学院山西煤炭化学研究所 | Superfine catalyst for preparing methyl formate by carbonylating methanol |
| US9944587B2 (en) | 2014-01-07 | 2018-04-17 | Fujian Institute Of Research On The Structure Of Matter, Chinese Academy Of Sciences | Process for vapor-phase methanol carbonylation to methyl formate, a catalyst used in the process and a method for preparing the catalyst |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4100360A (en) * | 1977-02-28 | 1978-07-11 | E. I. Du Pont De Nemours And Company | Process for making lower alkyl formates |
| DE3037089A1 (en) * | 1980-10-01 | 1982-05-06 | Basf Ag, 6700 Ludwigshafen | METHOD FOR PRODUCING METHYL FORMATE |
| DD207461A3 (en) * | 1982-04-12 | 1984-02-29 | Oleg A Tagaev | PROCESS FOR THE PREPARATION OF METHYL FORMAT |
| DE4237379A1 (en) * | 1992-11-05 | 1994-05-11 | Salzgitter Anlagenbau | A process for the production of methyl formate |
| CN1039711C (en) * | 1993-04-10 | 1998-09-09 | 中国科学院成都有机化学研究所 | Method and equipment for prodn. of methyl formate |
-
1996
- 1996-03-21 CN CN96103148A patent/CN1048656C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1085108C (en) * | 1998-06-10 | 2002-05-22 | 中国科学院山西煤炭化学研究所 | Superfine catalyst for preparing methyl formate by carbonylating methanol |
| US9944587B2 (en) | 2014-01-07 | 2018-04-17 | Fujian Institute Of Research On The Structure Of Matter, Chinese Academy Of Sciences | Process for vapor-phase methanol carbonylation to methyl formate, a catalyst used in the process and a method for preparing the catalyst |
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| Publication number | Publication date |
|---|---|
| CN1048656C (en) | 2000-01-26 |
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