CN102941112A - Novel catalyst for dehydrogenation preparation of formaldehyde by using methyl alcohol, preparation method and application of novel catalyst - Google Patents
Novel catalyst for dehydrogenation preparation of formaldehyde by using methyl alcohol, preparation method and application of novel catalyst Download PDFInfo
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- CN102941112A CN102941112A CN2012104753311A CN201210475331A CN102941112A CN 102941112 A CN102941112 A CN 102941112A CN 2012104753311 A CN2012104753311 A CN 2012104753311A CN 201210475331 A CN201210475331 A CN 201210475331A CN 102941112 A CN102941112 A CN 102941112A
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Abstract
The invention relates to a novel catalyst for dehydrogenation preparation of formaldehyde by using methyl alcohol, a preparation method and an application of the novel catalyst and belongs to the technical field of chemical engineering. The catalyst comprises components of 60-80% of anhydrous sodium carbonate and 20-40% of boric oxide; and the preparation method includes that the catalyst is obtained by means of mechanical mixing grinding and high temperature roasting methods. Process conditions of the prepared catalyst applied to dehydrogenation preparation of the formaldehyde by using the methyl alcohol include that the reaction temperature is 630-670 DEG C, the reaction pressure is ordinary pressure, a mixture of the methyl alcohol and nitrogen is used as a fed material, the mass percentage of the methyl alcohol is 0.24-0.27, and weight hourly space velocity of the methyl alcohol in the fed material is 1.16-3.86h<-1>. Under optimal reaction conditions, the conversion rate of the methyl alcohol reaches 59.97%, and selectivity of the formaldehyde reaches 83.28%.
Description
Technical field
The invention belongs to chemical technology field, be specifically related to a kind of Catalysts and its preparation method and technique for applying that is prepared anhydrous formaldehyde by methanol dehydrogenation.
Background technology
Formaldehyde is the important foundation raw material of chemical industry, and its purposes is very extensive, and the industrial preparative method of formaldehyde contains a large amount of water, the anhydrous formaldehyde that need to just can obtain having significant application value through comparatively complicated separation method.Industrial production anhydrous formaldehyde adopts two-step method usually: at first with methanol oxidation (iron-molybdenum method) or oxidative dehydrogenation (silver-colored method), generate water content up to the formalin more than 50%, and then concentrate formaldehyde with the technique of decompression distillation or solvent azeotropic, and because the formalin vapour pressure is very low, and relative ideal solution is certain minus deviation and forms azeotropic system, thereby in practical operation, the dehydration separating effect is not good, power consumption is huge, and production cost is high.Consider from economic benefit and technical process, if can prepare anhydrous formaldehyde by the methyl alcohol direct dehydrogenation, then can avoid the shortcoming of oxidizing process, product formaldehyde is easy to separate with accessory substance hydrogen, can not only obtain high-quality hydrogen and avoid the lock out operation of formalin, has simplified process route, it is the direction that will prepare from now on anhydrous formaldehyde, but the methyl alcohol direct dehydrogenation is produced anhydrous formaldehyde, suitability for industrialized production that so far there are no, and the selection of catalyst is the key of this novel process route.
Existing patent examined patent publication 41-11853 report by the catalyst that is formed by copper, silver, silicon, examined patent publication 47-19251 with the catalyst of the alloy composition of zinc, potassium, indium or the aluminium of melting or these metals, examined patent publication 48-97808 with the molten zinc of carbon containing or contain the catalyst of alloy composition of zinc and the catalyst that examined patent publication 52-215 forms with copper, zinc, selenium etc., but mostly the life-span is short, reactivity is low for the catalyst that these methods obtain, and does not have industrial application value.And the catalyst that the catalyst that examined patent publication 51-1407 is comprised of copper, zinc, sulphur and examined patent publication 51-76209 are comprised of copper, zinc, supply with gaseous sulphide and carry out methanol dehydrogenation, in reaction product or Exhaust Gas, sneak into sulphur, owing to the problems such as environmental pollution have limited its commercial Application.A kind of use of catalyst containing sodium makes the formaldehyde yield bring up to 70%(Appl.Catal.A:Gen., and 2001 (213) 203), but owing to the problems such as its catalyst life and regeneration are restricted its industrial applications.The Ag-SiO of Japan Patent (examined patent publication 60-89441) report
2-ZnO catalyst has obtained 69.4% methanol conversion and 51.8% formaldehyde yield, and the major defect of this catalyst is that the existence at surface alkalinty center causes the generation of accessory substance CO and makes the selectively on the low side of catalyst PARA FORMALDEHYDE PRILLS(91,95).Chinese patent CN200310108127.7 and CN200310108720.1 adopt the Ag-SiO of sol-gel process (SOL-GEL method) preparation
2-MgO-Al
2O
3, Ag-SiO
2-Al
2O
3The yield of-ZnO formaldehyde can be up to 95.6%, because the problems such as its reaction temperature and catalyst life and regeneration have limited its industrial applications.
In the catalyst of having studied, sodium carbonate is proved to be a kind of methanol dehydrogenation is prepared the effectively catalyst of anhydrous formaldehyde, and adopts merely sodium carbonate, its reaction temperature up to 700 ℃ or more than.
Summary of the invention
Content of the present invention provides a kind of take sodium carbonate as active constituent, boron oxide is the preparation method of the methanol dehydrogenation of auxiliary agent anhydrous formaldehyde new catalyst processed, adopt simple sodium carbonate to have the too high problem of reaction temperature to solve, and the conversion ratio of raising methyl alcohol and formaldehyde is selective.
Methanol dehydrogenation of the present invention prepares the catalyst of anhydrous formaldehyde, is that 60%～80% natrium carbonicum calcinatum and mass percent are that 20%～40% boron oxide forms by mass percent.
The preparation method of above-mentioned catalyst, grind the natrium carbonicum calcinatum of aforementioned proportion and two kinds of component mechanical mixture of a certain proportion of boric acid evenly after roastings, cooling compressing tablet, fragmentation, screenings namely get catalyst prod.
The technique for applying of above-mentioned catalyst: adopt the atmospheric fixed bed reactor of continuous-flow, reaction temperature is 600 ℃～700 ℃; Reactor feed is nitrogen and methanol liquid, and wherein the mass fraction of methyl alcohol is 0.24～0.27.The quartz tube reactor internal diameter is 9mm, catalyst amount 0.6g, and the methanol liquid inlet amount is 0.90mLh
-1～3.01mLh
-1, nitrogen (25～30 ℃) inlet amount is 1800～6000mLh
-1, the methyl alcohol weight (hourly) space velocity (WHSV) of charging is 1.16～3.86h
-1
Pure sodium carbonate is during as catalyst, its reaction temperature is higher, usually above 700 ℃, the present invention is take natrium carbonicum calcinatum as main active component, the adding boron oxide is co-catalyst, the catalyst that obtains makes the reaction temperature of methanol dehydrogenation anhydrous formaldehyde processed be reduced to 630 ℃～650 ℃, and reaction temperature obviously reduces, and methanol conversion and formaldehyde selectively all increase.
Figure of description
The XRD of 2# catalyst figure among Fig. 1 embodiment 2
The XRD of 3# catalyst figure among Fig. 2 embodiment 3
The XRD of 4# catalyst figure among Fig. 3 embodiment 4
The specific embodiment
Embodiment 1
Take natrium carbonicum calcinatum (analyzing pure) as active component, boron oxide as auxiliary agent, composition (quality %) is: sodium carbonate 80%, boron oxide 20%.Respectively take by weighing natrium carbonicum calcinatum 8.00g, boric acid (analyzing pure) 3.55g, after these two kinds of component mechanical mixture, in mortar, grind about 6h to evenly mix rear in tube furnace 400 ℃～500 ℃ roasting 2h, compressing tablet (tablet press machine pressure 15MPa), fragmentation, screening after the cooling, get 40～80 orders and get product, numbering 1# catalyst.
Embodiment 2
Process according to embodiment 1, respectively take by weighing natrium carbonicum calcinatum 7.50g, boric acid 4.44g, after these two kinds of component mechanical mixture, in mortar, grind about 6h to evenly mix rear in tube furnace 400 ℃～500 ℃ roasting 2h, compressing tablet (tablet press machine pressure 15MPa), fragmentation, screening are got 40～80 orders and are got product after the cooling.Its composition (quality %): sodium carbonate 75%, boron oxide 25%, numbering 2# catalyst.Fig. 1 is the XRD figure of 2# catalyst.
Embodiment 3
Process according to embodiment 1, respectively take by weighing natrium carbonicum calcinatum 7.00g, boric acid 5.33g, after these two kinds of component mechanical mixture, in mortar, grind about 6h to evenly mix rear in tube furnace 400 ℃～500 ℃ roasting 2h, compressing tablet (tablet press machine pressure 15MPa), fragmentation, screening are got 40～80 orders and are got product after the cooling.Its composition (quality %): sodium carbonate 70%, boron oxide 30%, numbering 3# catalyst.Fig. 2 is the XRD figure of 3# catalyst.
Embodiment 4
Process according to embodiment 1, respectively take by weighing natrium carbonicum calcinatum 6.50g, boric acid 6.22g, after these two kinds of component mechanical mixture, in mortar, grind about 6h to evenly mix rear in tube furnace 400 ℃～500 ℃ roasting 2h, compressing tablet (tablet press machine pressure 15MPa), fragmentation, screening are got 40～80 orders and are got product after the cooling.Its composition (quality %): sodium carbonate 65%, boron oxide 35%, numbering 4# catalyst.Fig. 3 is the XRD figure of 4# catalyst.
Embodiment 5
Process according to embodiment 1, respectively take by weighing natrium carbonicum calcinatum 6.00g, boric acid 7.10g, after these two kinds of component mechanical mixture, in mortar, grind about 6h to evenly mix rear in tube furnace 400 ℃～500 ℃ roasting 2h, compressing tablet (tablet press machine pressure 15MPa), fragmentation, screening are got 40～80 orders and are got product after the cooling.Its composition (quality %): sodium carbonate 60%, boron oxide 40%, numbering 5# catalyst.
Embodiment 6
Adopt the atmospheric fixed bed reactor of continuous-flow to investigate catalyst activity.Reactor is that an internal diameter is the quartz ampoule of 9mm, takes by weighing 1# catalyst 0.6g, places the reaction tube constant temperature zone, logical nitrogen (30mLmin
-1) at 600 ℃ of lower activation 1.5h; Furnace temperature is adjusted to 670 ℃ of reaction temperatures, passes into methanol liquid (2.28mLh by pump
-1), the rear nitrogen (4800mLh with passing into of vaporization
-1) be mixed into reactor, wherein the mass fraction of methyl alcohol is 0.26, the methyl alcohol weight (hourly) space velocity (WHSV) of charging is 2.94h
-1The 2# catalyst also adopts similarity condition to react, and the methanol dehydrogenation product is by gas chromatographic analysis.The reaction result of 1# and 2# catalyst sees Table 1.
Table 1 1# and 2# catalyst are 670 ℃ of catalytic activitys to methanol dehydrogenation formaldehyde processed
Embodiment 7
Adopt the same reactor of embodiment 6, take by weighing 3# catalyst 0.6g, place the reaction tube constant temperature zone, logical nitrogen (30mLmin
-1) at 600 ℃ of lower activation 1.5h; Furnace temperature is adjusted to 650 ℃ of reaction temperatures, passes into methanol liquid (2.28mLh by pump
-1), the rear nitrogen (4800mLh with passing into of vaporization
-1) be mixed into reactor, wherein the mass fraction of methyl alcohol is 0.26, the methyl alcohol weight (hourly) space velocity (WHSV) of charging is 2.94h
-1The 4# catalyst also adopts similarity condition to react, and the methanol dehydrogenation product is by gas chromatographic analysis.The reaction result of 3#, 4# and 5# catalyst sees Table 2.
Table 2 3#, 4# and 5# catalyst are 650 ℃ of catalytic activitys to methanol dehydrogenation formaldehyde processed
Embodiment 8
Adopt the same reactor of embodiment 6, take by weighing 3# catalyst 0.6g, place the reaction tube constant temperature zone, logical nitrogen (30mLmin
-1) at 600 ℃ of lower activation 1.5h; Keep 630 ℃ of reaction temperatures, pass into methanol liquid (0.9mLh by pump
-1), the rear nitrogen (1800mLh with passing into of vaporization
-1) be mixed into reactor, wherein the mass fraction of methyl alcohol is 0.24, the weight (hourly) space velocity (WHSV) of charging is 1.16h
-1Reaction result sees Table 3.
Table 3 3# catalyst is 630 ℃ of catalytic activitys to methanol dehydrogenation formaldehyde processed
Embodiment 9
Adopt the same reactor of embodiment 6, take by weighing 3# catalyst 0.6g, place the reaction tube constant temperature zone, logical nitrogen (30mLmin
-1) at 600 ℃ of lower activation 1.5h; Furnace temperature is adjusted to 670 ℃ of reaction temperatures, passes into methanol liquid (3.01mLh by pump
-1), the rear nitrogen (6000mLh with passing into of vaporization
-1) be mixed into reactor, wherein the mass fraction of methyl alcohol is 0.27, the weight (hourly) space velocity (WHSV) of charging is 3.86h
-1Reaction result sees Table 4.
Table 4 3# catalyst is 670 ℃ of catalytic activitys to methanol dehydrogenation formaldehyde processed
Take above-mentioned foundation desirable embodiment of the present invention as enlightenment, by above-mentioned description, the relevant staff can in the scope that does not depart from this invention technological thought, carry out various change and modification fully.The technical scope of this invention is not limited to the content on the specification, must determine its technical scope according to the claim scope.
Claims (3)
1. methanol dehydrogenation prepares the catalyst of anhydrous formaldehyde, it is characterized in that by mass percent be 60%～80% natrium carbonicum calcinatum, and mass percent is that 20%～40% boron oxide forms.
2. methanol dehydrogenation claimed in claim 1 prepares the preparation method of the catalyst of anhydrous formaldehyde, is characterised in that namely to get catalyst prod in 400 ℃～500 ℃ roastings, cooling compressing tablet, fragmentation, screening after natrium carbonicum calcinatum and two kinds of component mechanical mixture grindings evenly of boric acid.
3. methanol dehydrogenation claimed in claim 1 prepares the application of the catalyst of anhydrous formaldehyde: adopt the atmospheric fixed bed reactor of continuous-flow, reaction temperature is 630 ℃～670 ℃; Reactor feed is nitrogen and methanol liquid, and wherein the mass fraction of methyl alcohol is 0.24～0.27, and the methyl alcohol weight (hourly) space velocity (WHSV) of charging is 1.16～3.86h
-1
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| CN201210475331.1A CN102941112B (en) | 2012-11-21 | 2012-11-21 | Novel catalyst for dehydrogenation preparation of formaldehyde by using methyl alcohol, preparation method and application of novel catalyst |
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| CN201210475331.1A CN102941112B (en) | 2012-11-21 | 2012-11-21 | Novel catalyst for dehydrogenation preparation of formaldehyde by using methyl alcohol, preparation method and application of novel catalyst |
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| CN102941112B CN102941112B (en) | 2014-08-13 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105214583A (en) * | 2014-06-20 | 2016-01-06 | 中国科学院大连化学物理研究所 | A kind of microreactor for the reaction of methyl alcohol anaerobic dehydrogenation and Synthesis and applications thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06249842A (en) * | 1993-02-26 | 1994-09-09 | Sumitomo Metal Mining Co Ltd | Measurement of moisture in boric anhydride |
| CN101147872A (en) * | 2007-10-27 | 2008-03-26 | 太原理工大学 | Method for preparing anhydrous formaldehyde industrial catalyst by methanol dehydrogenation |
-
2012
- 2012-11-21 CN CN201210475331.1A patent/CN102941112B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06249842A (en) * | 1993-02-26 | 1994-09-09 | Sumitomo Metal Mining Co Ltd | Measurement of moisture in boric anhydride |
| CN101147872A (en) * | 2007-10-27 | 2008-03-26 | 太原理工大学 | Method for preparing anhydrous formaldehyde industrial catalyst by methanol dehydrogenation |
Non-Patent Citations (3)
| Title |
|---|
| ANDREAS MEYER 等: "Sodium compounds as catalyst for methanol dehydrogenation to water-free formaldehyde", 《CHEM.ENG.TECHNOL.》 * |
| SHOUJIN SU 等: "Catalytic Dehydrogenation of Methanol to Water-Free Formaldehyde", 《CHEM.ENG.TECHNOL.》 * |
| 杨怀旺 等: "甲醇脱氢制甲醛反应碳酸钠催化性能的研究", 《天然气化工》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105214583A (en) * | 2014-06-20 | 2016-01-06 | 中国科学院大连化学物理研究所 | A kind of microreactor for the reaction of methyl alcohol anaerobic dehydrogenation and Synthesis and applications thereof |
| CN105214583B (en) * | 2014-06-20 | 2017-05-17 | 中国科学院大连化学物理研究所 | Micro-reactor for anaerobic dehydrogenation reaction of methanol and preparation and application of micro-reactor |
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