EP0217855A1 - Verfahren und katalysator mit niedrigem natriumgehalt zur herstellung von formaldehyd aus methan - Google Patents

Verfahren und katalysator mit niedrigem natriumgehalt zur herstellung von formaldehyd aus methan

Info

Publication number
EP0217855A1
EP0217855A1 EP86902131A EP86902131A EP0217855A1 EP 0217855 A1 EP0217855 A1 EP 0217855A1 EP 86902131 A EP86902131 A EP 86902131A EP 86902131 A EP86902131 A EP 86902131A EP 0217855 A1 EP0217855 A1 EP 0217855A1
Authority
EP
European Patent Office
Prior art keywords
silica
catalyst
ppm
amount
moo
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP86902131A
Other languages
English (en)
French (fr)
Other versions
EP0217855A4 (de
Inventor
Nicholas David Spencer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
WR Grace and Co Conn
Original Assignee
WR Grace and Co Conn
WR Grace and Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US06/723,680 external-priority patent/US4607127A/en
Application filed by WR Grace and Co Conn, WR Grace and Co filed Critical WR Grace and Co Conn
Publication of EP0217855A1 publication Critical patent/EP0217855A1/de
Publication of EP0217855A4 publication Critical patent/EP0217855A4/de
Withdrawn legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/28—Molybdenum
    • 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
    • C07C45/33—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 CHx-moieties

Definitions

  • This invention relates to a highly selective method of producing formaldehyde, HCHO, by the partial oxidation of methane using a special type of catalyst and to a unique, highly selective formaldehyde-forming catalyst.
  • Products manufactured by oxidation of propane and butane include formaldehyde, acetaldehyde, acetone, propionaldehyde, methanol, n-propyl alcohol, isopropyl alochol, and butyl alchols.
  • the German Offerlegungsschrift 2,404,738 to Bayer discloses oxidizing methane to formaldehyde by using many different types of metal oxides which may be placed on many different types of supports.
  • the metal oxides are in Groups V, VI and/or VII of the Periodic Table. Among those listed are oxides of vanadium, niobium, tantalum, chromium, uranium, molybdenum, tungsten, manganese, technetium and rhenium, mixtures of these oxides with each other, and mixtures of these oxides with other oxides such as silica, alumina, iron oxide, calcium, oxide, magnesia, sodium oxide or potassium oxide.
  • the catalyst is 10 wt% Mo as MoO 3 on silica.
  • U. S. Patent No. 3,996,294, to Imre et al and assigned to Eayer discloses the use of a silica catalyst which does not contain any molybdenum to produce formaldehyde from methane.
  • a catalyst consisting purely of silica such as Cabosil (a product of Cabot Corporation)
  • Cabosil a product of Cabot Corporation
  • Some of the examples in the Imre et al patent employ catalysts made substantially of silica along with small amounts of other metal oxides.
  • molybdenum oxide Although, as in the companion German Offenlegungsschrift, there is a broad list of metal oxides which can be used, including oxides of aluminum, iron, vanadium, molybdenum. tungsten, calcium, magnesium, sodium or potassium with a specific reference that up to 5% of Na 2 O can be used.
  • Japanese Patent Publication 58-92629 discloses a SiO 2 -MoO 3 catalyst, using N 2 O or oxygen as oxidants. They report negligible selectivity to methanol or formaldehyde in the case of O 2 oxidation.
  • a molybdena-silica catalyst is described, which also uses nitrous oxide for the partial oxidation of methane to formaldehyde and methanol.
  • N 2 O as an oxidant is prohibitively expensive.
  • the silica in the catalyst is a fumed silica which is an expensive form of silica.
  • British Patent 1398385 discloses a methane partial oxidation catalyst consisting of MoO 3 and CuO in the absence of carrier or binder. The inventors state, however, that the presence of at least 2 vol. % of a higher hydrocarbon must be present for the process to be effective, and their principal oxygenated product is methanol. Formaldehyde selectivity reaches a maximum of 15.5%
  • British Patent 1244001 discloses several catalysts for the partial oxidation of hydrocarbons. All of these catalysts contain MoO 3 . The inventors claim that the principal oxygenated product is methanol, and the maximum selectivity to formaldehyde is 8%.
  • a catalytic process has been developed which converts methane to formaldehyde with high selectivity.
  • a catalyst which is made of molybdenum trioxide, MoO 3 , supported on silicon dioxide (silica) containing low levels of sodium,
  • MoO 3 molybdenum trioxide
  • the molybdenum trioxide is present in concentrations from a catalytically effective amount to 50 wt. % Mo, and especially preferred values are between about 0.5 wt. % and 15 wt. % Mo.
  • MoO 3 loadings such as greater than 15 wt. % Mo could be used, such catalysts rapidly lose MoO 3 due to sublimation. Because this sublimation loss could have serious consequences on downstream processes, such high MoO 3 loadings are not preferred.
  • the silica support can have a surface area in the range of 20-1000 m 2 /g, and more preferably in the range of 30-600 m 2 /g.
  • the silica support should contain a low amount of sodium such as in the range of between 0 and 350 ppm Na, preferably between 0 ppm and
  • silica 100 ppm Na and most preferably between 0 and 20 ppm Na or at a level of 1 ppm or less.
  • Commercially available and relatively inexpensive forms of silica such as silica gel or precipitated silica can be used and treated with an acid wash to remove the excess sodium.
  • a novel MoO 3 containing catalyst which provides the highest selectivity for converting methane to formaldehyde utilizes an ultrapure silica support which has a silica content of at least 99.99 wt% silica and a sodium content of less than 50 ppm. More preferably forms have sodium contents of less than 4 ppm and more preferably less than 2 ppm.
  • These catalysts provide very high turnover numbers on the order of 38 micromoles of formaldehyde per square meter of catalyst per hour. Such a turnover rate is approximatley 6 times higher than similar MoO 3 loaded catalysts where the support is a fumed silica. Higher turnover numbers are advantageous, since they allow reactors to be reduced in size, with a consequent decrease in capital outlay.
  • the present invention discloses the ability to have methane converted to formaldehyde with a high selectivity by reacting methane simultaneously with a molecular oxygen containing gas when employing a catalyst having a catalytically effective amount of MoO 3 on a silica support where the silica support is critically selected such that it has a sodium content of less than 350 ppm Na.
  • this encompasses a broad range of silica supports.
  • Commercially available and relatively inexpensive forms of silica such as silica gel or precipitated silica can be used and treated with an acid wash to remove the excess sodium.
  • the preferred silica supports is an ultrapure silica having a SiO 2 content of at least 99.99 wt%. This silica can be prepared by the hydrolysis of a silicon tetraalkoxide. A catalyst made from this ultrapure support is shown to have the highest selectively and the highest turnover numbers.
  • the catalyst can be prepared by either the incipient wetness technique or by evaporation to dryness of a slurry of the low sodium form of silica in a molybdenum-containing solution.
  • particles of silica are impregnated by an amount of a molybdenum-containing solution equal to the pore volume of the silica being impregnated.
  • the particles of silica are placed in a volume of aqueous molybdenum-containing solution and the solvent evaporated.
  • the catalyst is in a powder form, it can be pelleted, crushed and screened to obtain uniform size particles for loading into the reactor.
  • the size of the particles can be adjusted and selected depending on the geometry of the reactor.
  • molybdenum for impregnation is ammonium paramolybdate, which dissolves in water or in a very dilute hydrogen peroxide solution.
  • Other possible molybdenum salts would include molybdenum oxalate and possible phosphomolybdic acid.
  • the catalysts produced by either of these preferred methods have the molybdenum trioxide, MoO 3 , present in concentrations between a catalytically effective amount which can be as low as 0.5 wt. % and 50 wt. % Mo, and especially preferred values are between 0.5 wt. % and 15 wt. % Mo.
  • MoO 3 molybdenum trioxide
  • silica component must possess a low sodium level.
  • This result may be achieved by using silica with an intrinsically low sodium level such as Cabosil, a product of Cabot Corporation, or by removing sodium from a form of silica with an intrinsically high sodium level such as Intermediate Density ("ID") Silica Gel or a precipitated silica such as Sylox-15. Both of these products are made by the Davison Chemical Division of W. R. Grace & Co.
  • a further way to achieve the low sodium level is to use an ultrapure form of silica which has a SiO 2 content of at least 99.99 wt. %. This can be made, for example, by the hydrolysis of a silicon tetraalkoxide.
  • the silica should ultimately have a sodium content in a range of between 0 and 350 ppm Na, preferably between 0 ppm and 100 ppm Na and most preferably between 0 and 20 ppm Na or at a level of 1 ppm or less.
  • the surface area of the silica is in the range of 20-1000 m 2 /g, preferably between 30 m 2 /g and 600 m 2 /g.
  • the catalyst can be used to oxidize methane to formaldehyde at temperatures preferably between 500 and 700°C, a variety of pressures including atmospheric, space velocities between 1,000 and 20,000 hr (GHSV at NTP) and gas compositions from 0.5% O 2 (as oxygen or air) in CH 4 to the upper explosion limit which is dependent on pressure and concentration of inerts as discussed by C. M. Cooper and P. J. Weizevich, Ind. Eng. Chem., 21, (1929) 1210. Under optimal conditions, formaldehyde selectivities in excess of 90% (carbon basis) can be obtained.
  • the oxygen consumption value is determined as the difference between the inlet and outlet oxygen concentrations.
  • the catalysts made according to the present invention desirably have selectivities of greater than 40%.
  • the ultrapure silica support is preferably made by hydrolyzing an alcoholic solution of a silicon tetraalkoxide such as silicon tetraethoxide, followed by slow drying and calcination.
  • This example illustrates the preparation of a catalyst using an ultrapure form of silica.
  • the ultrapure material was made by dissolving 104 g silicon tetraethoxide in 104 g ethanol. Concentrated ammonia solution was added to the mixture until the pH exceeded 9.0. Gellation began to occur immediately, and the supernatant was allowed to evaporate overnight.
  • the gel was dried at 70° for 5 days in air, followed by calcination at 500°C for 2 hours in air.
  • a catalyst was prepared by impregnating 5 g of the silica thus formed by incipient wetness with 0.158 g ammonium paramolybdate 4-hydrate and calcining at 482°C for three hours.
  • the resulting catalyst had a molybdenum loading of 1.6 wt% and sodium level below the detection limit of inductively-coupled plasma analysis techniques.
  • the BET surface area was 47 m 2 /g .
  • the catalyst was pressed together, crushed and screened to US 25-35.
  • This example illustrates the preparation of a catalyst using a fumed silica.
  • the catalyst was prepared by impregnating 50 g. of
  • This example illustrates the preparation of a catalyst using an acid washed silica gel.
  • the resulting catalyst had a surface area of 232 m 2 /g, a molybdenum loading of 8.63 wt.% and a sodium level less than 20 ppm.
  • This catalyst was prepared using a commercially available silica gel where the sodium content was not reduced.
  • Example 4 A commercial grade silica gel, "Davison "ID", manufactured by the Davison Chemical Division of W. R. Grace & Co., was used without further processing.
  • a catalyst based on this material was prepared by following the method of Example 2 with the exception that the H 2 SO 4 treatment, which lowers sodium content, was not carried out.
  • the resulting catalyst had a molybdenum loading of 9.7 wt.%, a sodium level of 520 ppm and a surface area of 282 m 2 /g (BET).
  • BET surface area of 282 m 2 /g
  • This example illustrates the preparation of a catalyst using an acid washed precipitated silica.
  • Example 5 This example illustrates the preparation of a catalyst using an acid washed silica gel having a lower Mo loading.
  • An acid washed silica gel catalyst was prepared according to the procedure in Example 3 except that the molybdenum loading was controlled to be only 1.8% Mo and the sodium level was reduced to 1 ppm.
  • This example illustrates the preparation of a comparison catalyst using alumina as a support.
  • This example sets forth the evaluation of the catalysts made in Examples 1-6, Comparison Example 1, pure Cabosil, and the ultrapure support material made in Example 1 without any MoO 3 .
  • a 0.20 g (approx. 0.54 cc) sample of the screened catalyst was placed on a ⁇ uartz frit in a 3/8" O.D. ⁇ uartz tube and covered with 0.2 g US 25-35 screened quartz, which formed a preheating zone.
  • a thermocouple was inserted into the bed such that its tip was at the entrance to the catalyst section.
  • Gas mixtures consisting of 95% methane and 5% oxygen and 90% methane and 10% oxygen, were passed through the tube at 1 atm, at gas hourly space velocities of 2500-10,000 hr (NTP) while the tube was heated to 575°, 600°, 625° and 650°C.
  • the exit gases passed through heat traced Teflon (R) lines to a gas chromatograph where formaldehyde and carbon dioxide were analyzed in a Poropak T column in series with a methanizer and flame ionization detector. Other gases were analyzed using a thermal conductivity detector with a carbosphere column.
  • the methanizer had been calibrated for formaldehyde against the chromatropic acid method. See West, P. W. and Sen B., Z. Anal. Chem. 153 (1956) 177-183.
  • Table 1 oxygen consumption is defined as the difference between the inlet and outlet oxygen concentrations at an operating pressure of 1 atm.
  • the selectivity to the formaldehyde intermediate decreases because more of the final end products of CO, CO 2 and H 2 O are formed.
  • the selectivity appeared to be a function of oxygen consumption, irrespective of the combination of temperatures and space velocities necessary to achieve this consumption.
  • the catalysts were also evaluated with a feed stream of 10% O 2 in methane, at 650°C, at 2500 hr (GHSV, NTP) , and at 1 atm.
  • the % methane conversion as determined by gas chromatography and the turnover number in micromoles methane converted per square meter of catalyst per hour (a measure of specific activity) are set forth in Table 2.
  • the ultrapure silica-supported molybdena catalyst has an exceptionally high specific activity.
  • the molybdena- containing catalysts have activities which are higher than those of silica-only catalysts and the acid washed silica gel-supported molybdena catalyst has more than twice the specific activity of the "as received" silica gel-supported molybdena catalyst.
  • the alumina-supported catalyst also has a high specific activity but as was set forth in Table 1, it produces no detectable formaldehyde and the methane is principally oxidized to carbon oxides and water.
  • Cabosil has less than 4 ppm Na and thus a sodium-loaded version was made by washing it in a dilute solution of sodium hydroxide having a pH of 10.2 at 100°C.
  • Silica gel contains substantial sodium as manufactured.
  • Low-sodium versions were made by washing in dilute H 2 SO 4 having a pH of 3 at different temperatures.
  • the supports were made into catalysts using the method of Example 2 for the treated and untreated Cabosil and the method of Example 3 for the treated and untreated silica gels. The catalysts were tested according to the procedure in Example 7 and the results are set forth in Table 3.
  • Examples 12 and 13 These examples illustrate the efficiency of catalysts having low MoO 3 loadings on silica for the partial oxidation of methane.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
EP19860902131 1985-04-16 1986-03-05 Verfahren und katalysator mit niedrigem natriumgehalt zur herstellung von formaldehyd aus methan. Withdrawn EP0217855A4 (de)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US72368185A 1985-04-16 1985-04-16
US06/723,680 US4607127A (en) 1985-04-16 1985-04-16 Process and catalyst for the production of formaldehyde from methane
US723681 1985-04-16
US723680 1985-04-16

Publications (2)

Publication Number Publication Date
EP0217855A1 true EP0217855A1 (de) 1987-04-15
EP0217855A4 EP0217855A4 (de) 1988-11-29

Family

ID=27110845

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19860902131 Withdrawn EP0217855A4 (de) 1985-04-16 1986-03-05 Verfahren und katalysator mit niedrigem natriumgehalt zur herstellung von formaldehyd aus methan.

Country Status (7)

Country Link
EP (1) EP0217855A4 (de)
CN (1) CN86102245A (de)
AU (1) AU5546786A (de)
CA (1) CA1259299A (de)
ES (1) ES8706597A1 (de)
NO (1) NO861233L (de)
WO (1) WO1986006063A1 (de)

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6028228A (en) * 1997-09-26 2000-02-22 Georgia-Pacific Corporation Production of formaldehyde from CH4 and H2 S
ITMI981633A1 (it) * 1998-07-16 2000-01-16 Enitecnologie Spa Catalizzatore a base di molibdeno e suo impiego nell'isomerizzazione di n-paraffine
CA2343836C (en) 1998-09-14 2007-12-04 Shell Internationale Research Maatschappij B.V. Epoxidation catalyst carrier, preparation and use thereof
US7232786B2 (en) 1998-09-14 2007-06-19 Shell Oil Company Catalyst composition
US7232918B2 (en) 2001-11-06 2007-06-19 Shell Oil Company Catalyst composition
US7504525B2 (en) 1998-09-14 2009-03-17 Shell Oil Company Catalyst composition
WO2000056692A1 (en) * 1999-03-24 2000-09-28 Lehigh University Production of formaldehyde from ch4 and h2s
EP1038578A3 (de) * 1999-03-26 2002-01-30 President of Shizuoka University, a government agency of Japan Verfahren zur direkten Herstellung von Formaldehyd aus Methan
AU747541B2 (en) * 2000-03-27 2002-05-16 President Of Shizuoka University Method of producing formaldehyde directly from methane
RU2283829C1 (ru) * 2005-02-24 2006-09-20 Институт химической физики им. Н.Н. Семенова РАН (ИХФ РАН) Способ производства формальдегида
EP2125202A2 (de) 2006-11-20 2009-12-02 Shell Internationale Research Maatschappij B.V. Verfahren zur behandlung eines trägers, verfahren zur herstellung eines katalysators, katalysator und verwendung des katalysators
CN101723794A (zh) * 2008-10-13 2010-06-09 微宏动力系统（湖州）有限公司 甲烷制备溴甲烷、乙酰溴、醋酸和醋酸酯的方法
US12379376B2 (en) 2018-12-03 2025-08-05 University Of Notre Dame Du Lac Biosensor and method for detection of analytes

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US2102160A (en) * 1933-03-15 1937-12-14 Firm Gutehoffnungshutte Oberha Process for the production of formaldehyde from methane
US2381825A (en) * 1939-04-29 1945-08-07 Universal Oil Prod Co Catalytic conversion process
US2376668A (en) * 1942-04-16 1945-05-22 Monsanto Chemicals Process for production of formaldehyde
US2625519A (en) * 1950-03-07 1953-01-13 Du Pont Oxidation catalysts
GB1244001A (en) * 1968-05-01 1971-08-25 Ici Ltd Oxygenated hydrocarbons production
DE1940259A1 (de) * 1969-02-13 1970-10-22 Nat Res Dev Verfahren zur Oxydation von Alkanen
GB1398385A (en) * 1971-09-08 1975-06-18 British Gas Corp Oxidation of gases which consist principally of hydrocarbons
DE2404738A1 (de) * 1974-02-01 1975-08-21 Bayer Ag Verfahren zur herstellung von formaldehyd
DE2404737A1 (de) * 1974-02-01 1975-08-21 Bayer Ag Verfahren zur herstellung von formaldehyd
CH611576A5 (de) * 1975-06-26 1979-06-15 Buehler Ag Geb
DE2743113C3 (de) * 1977-09-24 1980-09-04 Chemische Werke Huels Ag, 4370 Marl Verfahren zur Herstellung von Gemischen aus Formaldehyd und Methanol durch partielle Oxidation von Methan
US4280929A (en) * 1979-09-17 1981-07-28 Standard Oil Company Attrition resistant-higher active component fluid bed catalysts
JPS5892629A (ja) * 1981-11-27 1983-06-02 Masakazu Iwamoto メタンの部分配化によるメタノールおよびホルムアルデヒドの製速造方法
US4455390A (en) * 1982-08-19 1984-06-19 Union Oil Company Of California Catalyst and method for impregnating at a pH less than one

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
No relevant documents have been disclosed. *
See also references of WO8606063A1 *

Also Published As

Publication number Publication date
NO861233L (no) 1986-10-17
EP0217855A4 (de) 1988-11-29
ES8706597A1 (es) 1987-07-01
WO1986006063A1 (en) 1986-10-23
CA1259299A (en) 1989-09-12
AU5546786A (en) 1986-11-05
CN86102245A (zh) 1986-10-15
ES554421A0 (es) 1987-07-01

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