JPS5954612A - Crystalline lamellar zirconium phosphate and preparation of lower olefin using said compound as catalyst - Google Patents

Abstract

PURPOSE:To prepare a lower olefin in high efficiency, by contacting methanol, etc., with a crystalline zirconium phosphate containing organic amine and obtained from a dihydrogen alkyl ammonium phosphate and zirconium oxychloride. CONSTITUTION:A dihydrogen alkyl ammonium phosphate and zirconium oxychloride are subjected to hydrothermal reaction to obtain a crystalline zirconium phosphate of Zr(R3NH)xH2-x(PO4)2.nH2O (X is 0-2; R3N is tertiary organic amine) containing organic amine between layers and having a laminer spacing of >=13Angstrom . A lower olefin can be prepared in high efficiency by contacting methanol or dimethyl ether with the zirconium phosphate prepared by the above process.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an improved crystalline zirconium phosphate and a method for producing lower olefins using the same as a catalyst.

Methanol and dimethyl ether can be converted to monohydrocarbon mixtures using structurally ordered solid acid catalysts such as zeolites or heteropolyacids. However, these methods have the drawback of producing a large amount of paraffinic hydrocarbons having 4 or more carbon atoms. In addition, the preparation of catalysts with high selectivity for desirable olefinic hydrocarbons requires relatively expensive and specialized reagents.

In order to overcome these drawbacks, the present inventors conducted various studies and discovered a method for producing lower olefins from methanol and dimethyl ether (using a layered phosphate catalyst having one structural rule) (patent application). Showa 57-1723
4).

However, in order to obtain high conversion rates, it is necessary to have a larger interlayer distance. In view of these circumstances, the inventors of the present invention have conducted extensive research and have discovered a new method for producing structurally ordered layered phosphates: 1. (1) By hydrothermally reacting these and zirconium oxychloride), a material having a thicker interlayer distance than T-zirconium phosphate (interlayer distance 1 = tz, zA), ti, two-layered diphosphoric acid...-lam is found to be Ie)
To reach the point.

The present invention's diyl arinate salt has the compositional formula-': Zr
(between R3), i (>, -, jt, , PO4) a
7njtxO (Ox', 2) It can be obtained by subjecting dihydrogen alkynogentium phosphate to oxyhydrogen zirconium or the like through a hydrothermal synthesis reaction.

As mentioned above, in the present invention, the organic amine is added to the metal part and the 13 A layer on the tatami, between the crystal + 'IJ, acid di~, omo, um? layers during hydrothermal synthesis production. A compound having a pressure front can be obtained.In the case of 9, the reaction 17W1 degree is i30'C or more (- is preferably used.

1 before the organic amine, 7) charcoal - (2 number [~
Those having 12 unsaturated alkyl radicals are generally applied. ':: Nizy organic amine-containing M crystal 1 produced according to the present study!
Zirconium 1 myphosphate is a solid acid with an interlayer distance of 113 A□ or more (methanol and dimethyl ether). 1 ethylene by contacting the crystalline phosphate prepared according to the present invention with 1, meth, ,/- or dimethyl ether in the liquid phase or preferably in the gas phase at elevated temperature. and hydrocarbons rich in olefins such as propylene. When producing olefins, the reaction temperature is 250 to 400°C, preferably 340 to 380°C.
A range of 0 °C is preferred. If the temperature is too low, ether,
Both of these are unfavorable, since there is a large amount of by-products, which lowers the yield of the desired lower olefin, and (if the temperature is too high), the structure of the crystalline layered phosphate may change. The reaction pressure is preferably normal pressure, but it can also be carried out under reduced pressure.

The catalyst is generally used in the form of one fixed bed. The space velocity of the reactants on the catalyst can be changed as appropriate and is usually within the range of 1 to 100 moles/JII catalyst per hour.

During contact, the reaction gas may be diluted with an inert gas or water vapor.

Next, the present invention will be explained in more detail with reference to Examples.

Example 1 Add 10'i, , 19 g of triethylamine to 3Q
8596 phosphoric acid 1. ,,
,,． 15g and a small amount as needed1. Steam 1iJ (water (
Add about 2 o, ml, ) and boil the contents: Q < 1
? 1l14(ζvacuum dihydrogen sulfate 1)ethyl 77-T:
Nium ((CJI 5 )3N11 (,Hfu,07
)) was obtained. Next, wash 8.ki, and the humidity is 75-78.
! 5.8 g of product 11 was obtained in 1 liter of 6 chambers. As a result of chemical analysis, the Ja4 product was Zrf(c
, t+.

N1ρio,'5 1. +, 5(R04)2' ””0
．． ! ';) IzO's FtllJ is now available,, xi
By Izumi diffraction, the interlayer separation i13. '(] □ Su de: □ Tsuta.

i:) 1 piece of phosphorus-zircoium containing triethylamine 4'I] was molded into a 1.0-20 mesh 1 piece, and inside'
(%'10 l+1m fi' stainless steel flow 1iT
The mixture was filled into a J-type reaction tube. For heating, use 11 degrees of frill.
The temperature error was kept at 15°C by using an electric furnace equipped with a furnace.

Prior to the reaction, Al=+”y was 10+n at 300°C.
Pretreatment was carried out by flowing for 3 hours at a flow rate of 11 l/min. 1 jil
After treatment, methanol was supplied at a rate of 4 ml per hour, and the reaction was carried out at normal pressure and 300 to 380°C. The reaction product was analyzed using a one-game chromatograph using argon supplied together with methanol as an internal standard. Conversion rate of methanol and carbon number 5 excluding dimethyl ether
The table shows the proportion of hydrocarbons and olefins in the following products:

For comparison, a case in which commonly known zirconium terphosphate is used as a catalyst is also shown. 20
After the reaction time, the accumulation of carbonaceous material on the catalyst increases with the catalyst Φ,'
) per iii, 1 wt96.

Example 2 Tri-11-propylamino 143 (as tertiary amine)
The interlayer distance was 13,674.

The reaction was carried out in the same manner as in Example 1 using 4 ml of the obtained tri-n-propylamine-containing zirconium phosphate as a catalyst: 1FT? 'L, Fζ. The reaction results are shown in the table. 2
After 0 hours of reaction, the accumulation of char on the catalyst was 6.3 wt9(i) per catalyst weight.

Example 3 Same as Actual Gun Example 1 except that 185°36 g of 1tri-n-butylamine was used as the tertiary amine.
A J-quality zirconium phosphate containing tri+1-butylamine was obtained.

11) The reaction was carried out in the same manner as in 17-h1 Example J using 11-butylamine-containing zirconium phosphate A4m1 as a catalyst. The reaction results are shown in the table. After 20 hours of reaction, the accumulation of charcoal and genus on the catalyst 1-,
j: &l! It was 3.0 wt95 per medium weight.

-) Other reaction conditions: normal pressure, L) ISV-1hr
-'DMg-nidimethyl ether 4C5: To substances with carbon number of 5 or less In addition to hydrocarbons, C0NC
X-mass containing O2: Carbon base within the Institute of Chemical Technology, 1-1 Higashi, Yatabe-cho, Tsukuba-gun, Ibaraki Prefecture

Claims (1)

[Claims] (1) A crystalline zirconium phosphate obtained by hydrothermally reacting a dihydrogen alkylammonium phosphate and a zirconium oxychloride, containing an organic amine between the layers and having an interlayer distance of 13A or more. (2. A method for producing crystalline relefin obtained in claim 1.