Heteropoly acid/multimetal oxacid salt catalyst

A technology of polyoxometalates and heteropolyacids, applied in metal/metal oxide/metal hydroxide catalysts, physical/chemical process catalysts, catalyst activation/preparation, etc. The method of salt carrier pore size and other issues

Inactive Publication Date: 2001-02-21
ROHM & HAAS CO +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

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  • Heteropoly acid/multimetal oxacid salt catalyst
  • Heteropoly acid/multimetal oxacid salt catalyst
  • Heteropoly acid/multimetal oxacid salt catalyst

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0110] The heteropolyacid catalyst and polyoxometallate support were prepared according to the following general procedures.

[0111] Heteropolyacids

[0112] Phosphotungstic acid and phosphomolybdic acid used in the following examples, H 3 PW 12 o 40 and H 3 PMo 12 o 40 purchased for the market.

[0113] H used in the following examples 3+x (PM 12-x V x o 40 )-type catalysts are prepared by the following general procedure, with H 5 PV 2 Mo 10 o 40 for example. h 5 PV 2 Mo 10 o 40 Prepared by the following method: 48.8g NaVO in 200g deionized water 3 and 14.2g Na in 200g deionized water 2 HPO 4 Mix at 95°C. After the mixture had cooled, 18.4 g of concentrated sulfuric acid was added, at which point the solution turned red and an exotherm was observed. With the addition of acid, the pH dropped from 9.1 to 3.7. Then Na 2 MoO 4 400 g of deionized water was added, followed by 312 g of concentrated sulfuric acid, keeping the temperature below 50°C during t...

Embodiment 2

[0132] The polyoxometalate-supported heteropolyacid catalysts used in the following examples were prepared in the following general steps to prepare H 3 PMo 12 o 40 / Cs 3 PMo 12 o 40 for example.

[0133] h 3 PMo 12 o 40 / Cs 3 PMo 12 o 40 (0.02 / 1.0 molar ratio - about 10% surface coverage) was prepared by the following method: 0.7196g H 3 PMo 12 o 40 20H 2 O, 34.02g Cs 3 PMo 12 o 40 Mix with 315g deionized water. After stirring at room temperature for 80 minutes, the water was removed by evaporation and the resulting solid was dried. The sample was heat treated in air at 150°C for 1 hour to yield 32.69 g of the desired catalyst. The catalyst is then pelletized to be filled in the oxidation reactor.

[0134] Examples of catalysts prepared according to this procedure are reported in Table 3, along with the approximate surface areas of the coated supports.

[0135] sample

[0136] Prepared four kinds of loaded Cs 3 PMo 12 o 40 (VO) on 1.5 PMo 1...

Embodiment 4

[0141] prepared two loaded Cs 3 PMo 12 o 40 (VO) on 1.5 PMo 12 o 40 catalyst samples. Each sample contains enough (VO) 1.5 PMo 12 o 40, so that 100% of the POM surface area is covered. As described in Example 3, one sample was heat treated at 300°C as a control. Another sample was heat treated in situ at 420°C in a catalytic reactor. The heat-treated samples were placed in a catalytic reactor under air at room temperature, propane was added to the reactor, and the temperature was raised to 420°C. The reactor was held at this temperature for less than 10 minutes and then cooled to 380°C to continue the reaction. The yield of acrylic acid at 30% propane conversion was determined. As described in Example 3, a control sample was also used to catalyze the conversion of propane to acrylic acid. The data for the control samples and the samples heat treated in situ are reported in Table 5.

[0142] temperature(℃)

[0143] The above data clearly show that in sit...

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Abstract

Disclosed are catalysts including a heteropolyacid supported on a polyoxometallate salt having increased yields, conversions and selectivities in the conversion of alkanes. Also disclosed are methods of preparing these catalysts.

Description

Background of the invention [0001] The present invention generally relates to improved catalysts for use in a wide variety of chemical processes. In particular, the present invention relates to improved catalysts comprising heteropolyacids supported on polyoxometallates. [0002] In general, it is well known that catalysts are useful in a wide variety of chemical processes, especially for the preparation of products such as alcohols, carboxylic acids, alkenes, alkynes, etc., from alkanes. Typically, such catalysts are heat-treated at very high temperatures for a period of time to remove binders or undesired impurities introduced during catalyst preparation to generate the desired compound or crystalline phase, or by sintering to increase the final catalyst particle size mechanical strength. See, eg, C.N. Satterfield, "Heterogeneous Catalysis in Practice", McGraw-Hill, New York, 1980, p. 75. [0003] Heteropolyacids and polyoxometalates are well known as catalysts in many ap...

Claims

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Application Information

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IPC IPC(8): B01J27/19B01J23/16B01J27/188B01J27/199B01J31/06B01J37/08C07B61/00C07C5/42C07C11/02C07C51/215C07C57/05
CPCC07C5/42C07C51/215B01J27/188C07C11/02C07C57/04B01J23/16B01J31/06B01J37/08
Inventor P·E·艾里斯S·卡玛卡R·D·林克三世J·E·莱昂斯N·N·麦克尼尔A·F·小沃尔普
Owner ROHM & HAAS CO
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