• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
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    • 专利摘要:
    The present invention relates to a catalyst for the production of aldehydes, especially in the production of formaldehyde and acetaldehyde, by selective oxidation of primary alcohols, preferably methanol or ethanol, with oxygen, said catalyst having spinel structure. The catalyst typically contains an Fe: + Vf * Mo _: + A, O4 spinel structure where A is a possible cation vacancy and where z = 3-q-x-y and q>
    公开号:SE534233C2
    申请号:SE1000070
    申请日:2010-01-26
    公开日:2011-06-07
    发明作者:Arne Andersson；Robert Haeggblad
    申请人:Formox Ab；
    IPC主号:
    专利说明:

    534 233 The catalyst used in the oxide process is a mixture of ferrous molybdate Fe 2 (MoO 4); and molybdenum trioxide MoOç, with a Mo: Fe atomic ratio between 2 and 3. In most aspects, the catalytic performance is satisfactory; the yield of the plant is high (88-93%) and neither molybdenum nor iron is toxic, which is desirable both for human and environmental reasons.
    In methanol oxidation, however, the catalyst is deactivated due to fl odor of molybdenum from the catalyst. Molybdenum is sublined from the upper part of the reactor where the methanol concentration is high at the same time as it decomposes in the lower parts of the reactor, resulting in needle-shaped MoO 2 crystals. The sublimation and condensation / decomposition of molybdenum results in a decrease in the catalytic activity as well as a decrease in the formaldehyde selectivity at the same time as the pressure difference across the reactor increases. Therefore, the catalyst must be replaced after about 1-2 years or t.o.m. after less than one year of use, depending on the reaction conditions.
    In order to increase the capacity of current industrial plants and reduce costs for future plants, it is desirable to increase formaldehyde production per reactor and unit of time. One possibility for this is to increase the methanol concentration at the inlet of the reactor. One possible consequence of an increased methanol concentration, however, is that the temperature in the hot spot increases because anol your methanol molecules must be converted. Since higher temperatures and higher methanol concentrations mean that molybdenum more easily escapes from the catalyst present, any attempt to increase the plant's productivity by increasing the methanol concentration at the inlet will pose a risk of accelerating the volatility of the molybdenum.
    For this reason, alternative catalysts which exhibit lower performance of the active substances are also of interest, provided that they are active and exhibit comparable formaldehyde selectivity.
    In addition, the amount of harmful substances used in the catalyst should be limited for environmental reasons.
    According to U.S. Patent 7,193,177, bulk metal vanadates are active and selective catalysts for methanol oxidation with formaldehyde selectivities between 89.3% and 96.6% at high degrees of methanol conversion. Although these catalysts show a high formaldehyde selectivity, there is little knowledge about the stability of the catalyst, especially with regard to the vanadium ability. In addition, the amount of toxic vanadium in the catalyst is usually high, which makes it a worse alternative than the commercial MoO3 / Fe2 (MoO4) catalyst.
    An object of the present invention is not only to provide a suitable catalyst for aldehyde production, especially formaldehyde or acetaldehyde preparation by oxidation of primary alcohols, especially methanol or ethanol oxidation, but also to provide a catalyst which exhibits high selectivity to aldehyde, preferably formaldehyde or acetaldehyde, which is stable and low in active ingredients and contains a limited amount of harmful substances.
    This object can be achieved with a catalyst according to the present invention, wherein the catalyst has a spinel structure, typically containing iron, oxygen, vanadium and / or molybdenum. The catalyst preferably has a spinel structure of the form FefVf + Mo , y and z may further be 1.4 S q <3.0 S x S 1.0 S y S 0.3, 0 S z S 0.9 or more specifically 0.57 z <1.0.75 and OSz <0.88, 1.14 yS0.3 and OSz <0.88, 0.57 Sx <1.0 3.0Sx <1.5.0 or 1.42 <q <3.0 S x <1.0 <y S 0.3 and 0 S z <0.88. The catalyst may have cation vacancies in the structure determined by the deviation from the stoichiometry of the spinels, which are determined by the valences of the metals contained therein and thus by the reaction conditions, i.e. the reaction temperature and the composition of the reacting gas. Cations of, for example, Al, Co, Cr, Cu, Mn, Zn and Ti can also form spinel structures with Fe and can thus also be used to advantage in catalysts for oxidation of primary alcohol to aldehyde. 534 233 The discovery that a catalyst with a spinel structure containing a combination of certain concentrations of iron, vanadium and / or molybdenum cations has all the desired properties is an unexpected turnaround. In addition to exhibiting high formaldehyde selectivity (> 90%) from methanol and oxygen in an inert substance, no wettability either from vanadium or from molybdenum of the catalyst in question could be detected after 5 days of use at 300 ° C with a surface gas containing 10% methanol and 10% oxygen in nitrogen. A further advantage of the present invention is that high selectivity catalysts can be prepared with a low content of vanadium compared to, for example, the catalyst disclosed in U.S. Patent 7,193.117, which makes the aforementioned catalyst more suitable from the environmental and marine aspects. .
    The catalyst with the chemical composition Fefl * Vf * Mo; * AzO4 is prepared by precipitation from a homogeneous aqueous solution containing the desired amount of Fe, V and Mo. The homogeneous solution is prepared from one, two or three separate aqueous solutions, containing dissolved Fe (NO3) 3-9H2O, NH4VO3 and (NH4) 6Mo7024 ~ 4 H2O, respectively, in appropriate concentrations.
    If it is desired to have more than one element in the catalyst, these two or three well-stirred solutions are mixed with each other before homogenization. If necessary, the solution can be heated and / or the pH can be lowered by the addition of acids such as HNO 3, H 2 SO 4 and / or HCl.
    A solid precipitate is obtained when the pH has been raised sufficiently by the addition of bases such as NH; and / or NaOH. If necessary, the separation of solid phase from liquid phase can be facilitated by increasing the size of the precipitate which is done by raising the temperature of the liquid containing the precipitate to 35-100 ° C, typically 40-70 ° C.
    The particles are separated by centrifugation and then washed with water and acetone. Alternatively, the particles can be separated by filtration and then washed with water and acetone. The particles obtained by centrifugation or filtration are then dried in an oven.
    Finally, the dried particles are calcined at a temperature of 300 to 650 ° C, preferably 400 to 550 ° C, in an atmosphere containing reducing agents such as e.g. H2 and / or CO together with 534 233 oxidizing agents such as H 2 O and / or CO 2 in one or more inert substances such as e.g. He, Ne, N; and / or Kr. The composition of the reducing, oxidizing and inert substances of the gas can vary between 0-50% by volume, 0-50% by volume and 99.99-0% by volume, respectively. The reduction usually takes at least three hours. The final catalyst has a specific surface area (BET) of 2-25 m 2 / g, preferably 3-10 m 2 / g and most preferably 4-7 m 2 / g.
    The present invention further relates to the use of said catalyst in a cooled tube reactor for selective methanol oxidation with oxygen to formaldehyde. In the gas mixture at the inlet of the reactor, the methanol concentration is 6 to 13% and the oxygen concentration is 8 to 15% together with an inert gas, usually nitrogen. The catalyst of the present invention can be used either alone or in combination with other catalysts at any location in the reactor.
    The present invention is further explained with reference to the accompanying embodiments which are to be considered as illustrative and in no way limiting.
    Example 1 illustrates the preparation of spinel phase catalysts.
    Example 2 is a comparative example illustrating the preparation of a FeVO4 catalyst.
    Example 3 illustrates the catalytic efficiency of a spinel phase catalysts.
    Example 4 illustrates the aging of spinel phase catalysts demonstrated by altering the specific activity and elemental composition before and after use in methanol oxidation.
    Example 5 is a comparative example illustrating the aging of triclinic phase FeVO4 catalyst (prepared in Example 2) illustrated by the change in specific activity and the elemental composition before and after use in methanol oxidation.
    Example 1 Preparation of spinel phase catalysts As described in Table 1, six samples were prepared by precipitation from a homogeneous aqueous solution containing only dissolved Fe (sample 1) or together with V (samples 2-5) or 534 233 together with both V and Mo (sample 6). . The homogeneous solution was prepared from one (sample 1), two (sample 2-5) or three (sample 6) separate aqueous solutions, a 0.5 M solution of Fe (NO 3) 3 -9H 2 O (Merck), a 0.04 M NH4VO3 (Merck) solution and a 0.5 M (NH4) 6Mo7O24 - 4 H2O (Riedel-de Haën). To prepare Samples 2-6, two or three well-stirred solutions were mixed together and the pH was lowered to 1.0 by the addition of 3 M HNO 3. Also for sample 1, the pH was lowered to 1.0. When all solutions reached the pH value 1.0, all solutions were homogeneous. A solid precipitate was obtained as the pH was raised to 4.0 by the addition of 3 M NH 3. Particle agglomeration was performed to stimulate the recovery of particles by heating the cloudy solution for 2 hours at a temperature of 50 ° C with stirring. The particles were separated by centrifugation (3000 rpm, 3 minutes) and washed three times with water, acetone and then water again. Finally, the samples were dried for 16 hours at 80 ° C and then reduced for 15 hours at 450 ° C in an atmosphere consisting of a mixture of Hz / HgO / Ar.
    The phase composition of the catalyst was determined by X-ray powder diffraction analysis (XRD) on a Seifert XRD 3000 TT diffractometer with Ni-filtered Cu Ka radiation and a rotating sample container. Data were collected between 5 and 80 degrees 26 in steps of 0.1 ° (2.0 seconds / step). From Table 1 it can be seen that all samples 1-6 were at the time of preparation single-phase with spinel structure of the form F e: * Vf "Mo§ * A, O 4 similar to Fe 3 O 4. The diffractogram of the newly prepared sample 3 can be seen in Fig. 1.
    Example 2 Preparation of FeVO4 Catalysts To allow comparisons between Samples 1-6 described in Example 1 and a known vanadate catalyst, equivanate (FeVO4) described in U.S. Patent 7,193,117 was prepared which was designated as Sample 7. The preparation was performed as described in Example 1 except for the final calcination. Instead of performing the calcination in a reducing atmosphere, the calcination was performed in air at 580 ° C for 6 hours. The resulting catalyst was triclin (P1) FeVO4, which was determined by X-ray diffraction and can be seen in Fig. 2. 534 233 Example 3 Catalytic efficiency of spinel phase catalysts The efficiency of methanol oxidation in samples 1-6 from Example 1 was measured in a stainless steel flask reactor. at 300 ° C at atmospheric pressure. To ensure isothermal conditions, the reactor was placed in an aluminum block which was placed in a tube furnace (tube fumace). Prior to the measurements, the catalyst was ground to a fine powder which was pressed into tablets, which were crumbled in a sieve into particles with diameters in the range 0.250-0.425 mm.
    The reactor was charged with the desired amount of catalyst. The catalyst was heated to the reaction temperature in a de of 80 ml / min Nz. When the reaction temperature reached 300 ° C, a fl fate of 10 ml / min oxygen and 10 ml / min gas phase methanol was added to the nitrogen fl fate. All catalysts were present in the reactor overnight and their activities and selectivities after 16 hours in the reactor are presented.
    The catalytic activities were determined at low methanol conversion rate (ensuring varying conditions, while selectivity data presented were collected at high methanol conversion rate (90%). Methanol, formaldehyde (FA), dimethyl ether (DME), methyl phonate (MF), dimethoxymethane (DMM) and CO on site with a gas chromatograph equipped with a Haysep C column and both an FID and a TCD detector.CO was analyzed on site with an IR instrument (Rosemount Binos 100) The results can be seen from Table 2.
    Example 4 The aging of the spinel phase catalyst is demonstrated by changing the specific activity and the element composition before and after use in methanol oxidation.
    For each of Samples 1-6, 0.02 g of the catalyst was treated for 5 days at 300 ° C in a yield of N; with 10% methanol and 10% oxygen. This amount of catalyst was chosen to ensure differential conversion of methanol (It has previously been reported that the loss of Mo is greatest at the inlet of the catalytic bed [A.
    Andersson, M. Hemelind, O. Augustsson, Catal. Today 112 (2006) 40]. An ICP-AES elemental analysis of the catalysts was performed before (freshly prepared catalyst) and after (use 534,233 catalyst). The specific activity of the samples 1-6 used was also measured as described in Example 3. The results can be seen in Table 3.
    Example 5 Aging of the FeVO4 catalyst in triclinic phase is illustrated by the change in the specific activity and elemental composition before and after use in methanol oxidation.
    Sample 7 was treated as described for Samples 1-6 in Example 4 above and an elemental analysis with ICP-AES was performed for both freshly prepared and used samples. The specific activity of the sample 7 used was also measured as described in Example 3.
    The results can be seen from Table 3. See also Figures 1 and 2.
    Table 1. Elemental composition (molar ratio) of the prepared catalysts and phase compositions determined by X-ray diffraction of the freshly prepared catalyst and 5 days in methanol oxidation (Methanol / Og / Ng = 10/10/80 vol.% At 300 ° C).
    Samples 1-6 are the Fe-V-Mo oxide spinel catalysts and Sample 7 is a triclinic FeVO4 catalyst.
    Prepared composition Phase composition Sample Formula VzFe Mo: F e Newly prepared Sample Used sample 1 Fewg A 0.010., 0.00 0.00 Spinel Spinel 2 FegyoVaoó A 09404 0.02 0.00 Spinel Spinel 3 Fe2.67V0_19 A 0.140., 0, 07 0,00 Spinell Spinell 4 Fe |, 94V0,97 A 0,090., 0,50 0,00 Spinell Spinell 5 FelßyVLy A 03604 1,00 0,00 Spinell Spinell 6 Fe2,33V0_19Mo0,28 A 03104 0,08 0, 12 Spinell Spinell 7 FeVO4 1.00 0.00 Triclin Spinell Table 2. Specific activity and selectivity for products for freshly prepared samples 1-6 measured at 300 ° C with an input fate consisting of 10% methanol and 10% O; in NZ. 534 233 specific activity a) seiemiviæt (%) b) Sample (mon / seagull) FA DME MF co .1 1.02 0 0 0 100 2 2.33 18.3 0.4 10.3 71.1 3 1, 60 90.6 0.9 0.9 7.6 4 1.63 81.9 0.7 2.4 15.0 s 1.42 70.1 0.6 2.5 26.8 6 0.62 83 , 8 4.0 6.0 6.2 a) Determined under different conditions (methanol conversion b) Selectivities to the products formaldehyde (FA), dimethyl ether (DME), methyl formate (MF) and carbon oxides (CO 2), measured at 90% methanol conversion. 534 233 10 Table 3. Catalyst saturation (molar ratio) before and after use in methanol oxidation measured by [CP-AES and the corresponding change in the specific activity (activity ratio).
    Use Prepared composition “Newly prepared catalyst Catalystb) Sample V: F e MozFe V: Fe MozFe V: Fe MozFe êlfllšlllïšåec) 1 O 0 0 0 0 0 N.D. 2 0.02 0 0.02 0 0.02 O 1.18 3 0.08 0 0.08 0 0.08 0 1.07 4 0.49 0 0.49 0 0.54 0 0.99 5 1 .00 0 1.04 0 1.04 0 1.04 6 0.08 0.12 0.08 0.12 0.08 0.12 1.45 7 1.00 0 0.96 0 0.89 0 0 , 62 a) The catalyst composition prepared in the synthesis. b) The catalyst composition after use in methanol oxidation for 5 days at 300 ° C with methanol / O 2 / N; = 10/10/80 vol .-%.
    °) Specific activity of catalyst used divided by the specific activity of a freshly prepared catalyst.
    权利要求:
    Claims (1)
    [1] 1. 10. 11. A catalyst for aldehyde production through selective oxidation of alkanol with oxygen, characterised in that said catalyst has a spinel structure.A catalyst according to claim 1, characterised in that said catalyst comprises iron.A catalyst according to claim 1 or 2, characterised in that said catalyst comprises oxygen. A catalyst according to any of the claims 1-3, characterised in that said catalyst comprises vanadium and/or molybdenum. A catalyst according to claim 1, characterised in that said catalyst comprises a Fe fl+Vf+Mo ÛAZO 4 spinel structure wherein A is an optional cation vacancy and wherein z = 3-q-x-y and q> SyS1and0Sz< 1.3 and2SaS3,3SbS5and3ScS6. A catalyst according to claim 5, characterised in that 1.4 S q < 3. A catalyst according to claim 5 or 6, characterised in that 0 S x S 1. A catalyst according to any of the claims 5-7, characterised in that 0 S y S 0.3. A catalyst according to any of the claims 5-8, characterised in that 0 S z S 0.9. A catalyst according to claim 1, characterised in that said aldehyde is formaldehyde andsaid alkanol is methanol. A catalyst according to claim 1, characterised in that said aldehyde is acetaldehyde and said alkanol is ethanol. 12. 13. 14. 15. 12 A catalyst according to claim 1, characterised in that said catalyst has a specific surface area (BET) of 2-25 m2/ g, more preferably 3-10 mZ/g, most preferably 4-7 m2/ g. A process for producing a catalyst according to any of the claims 1-12, characterised in thatsaid catalyst is prepared by precipitation from a homogenous Water solution containingdesired amounts of Fe, V and Mo, where said homogenous solution first is prepared fromone, two or three separate water solutions, containing dissolved Fe(NO3)3 - 9H2O, NH4VO3and (NH4)6Mo7O24 ~ addition of a base to said homogenous solution, formed precipitate is then separated from 4 H20, respectively, where after said precipitation is obtained by said solution, washed, dried and calcined at a temperature of 300 to 650°C, in an atmosphere of a reducing agent together With an oxidizing agent in one or more inert agents. Use of a catalyst according to any of the claims 1-12 in a cooled multi-tube reactor forselective oxidation of alkanol, preferably methanol or ethanol, with oxygen to aldehyde, preferably forrnaldehyde or acetaldehyde. Use according to claim 14, characterised in that said alkanol is methanol and is present inconcentrations of 6 to 13% and oxygen in concentrations of 8 to 15% in a gas mixture together With an inert gas, most typically nitrogen, at the inlet of the reactor.
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    引用文献:
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    SE1000070A|SE1000070A1|2010-01-26|2010-01-26|Catalyst for the preparation of aldehyde|SE1000070A| SE1000070A1|2010-01-26|2010-01-26|Catalyst for the preparation of aldehyde|
    ES11737352T| ES2859484T3|2010-01-26|2011-01-19|Use of a structured spinel catalyst for the production of aldehydes|
    PCT/SE2011/000007| WO2011093763A1|2010-01-26|2011-01-19|Spinel structured catalyst for aldehyde production|
    EP11737352.2A| EP2528883B1|2010-01-26|2011-01-19|Use of a spinel structured catalyst for aldehyde production|
    PL11737352T| PL2528883T3|2010-01-26|2011-01-19|Use of a spinel structured catalyst for aldehyde production|
    CN201180007361.3A| CN102811991B|2010-01-26|2011-01-19|For the spinel structure catalyst of aldehyde production|
    US13/520,083| US9056304B2|2010-01-26|2011-01-19|Spinel structured catalyst for aldehyde production|
    PT117373522T| PT2528883T|2010-01-26|2011-01-19|Spinel structured catalyst for aldehyde production|
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