Method for producing unsaturated aldehyde and unsaturated carboxylic acid

Patent metadata

Field	Value
Publication number	US-10428007-B2
Application number	US-201716082704-A
Country	US
Kind code	B2
Filing date	Oct 17, 2017
Priority date	Nov 1, 2016
Publication date	Oct 1, 2019
Grant date	Oct 1, 2019

Abstract

The present invention relates to a method for producing unsaturated aldehydes and unsaturated carboxylic acids. According to the present invention, a method for producing unsaturated aldehydes and unsaturated carboxylic acids which can impart activity and control temperature independently in fixed catalyst layer zones in a shell-and-tube reactor, thereby exhibiting improved yield and operation stability, is provided.

First claim

The invention claimed is:

1. A method for producing unsaturated aldehydes and unsaturated carboxylic acids corresponding to a raw material in which at least one compound selected from propylene, isobutylene, t-butyl alcohol, and methyl-t-butyl ether is added as the raw material and subjected to gas phase contact oxidation with molecular oxygen or a molecular oxygen-containing gas, using a fixed-bed multistage heat medium circulating type of multi-tubular shell-and-tube reactor filled with a catalyst,
wherein the multistage heat medium circulating type of multi-tubular shell-and-tube reactor includes a cylindrical shell, a plurality of tube sheets for separating the inside of the shell into a plurality of independent spaces, a baffle for dividing the plurality of independent spaces inside the shell into two spatially continuous zones, and a plurality of reaction tubes fixed to the inside of the shell while penetrating through the plurality of tube sheets and the baffle,
wherein, in the plurality of independent spaces inside the shell, heat transfer to the reaction tube is performed independently at a temperature of 280 to 400° C. by the flow of an independent heat medium,
wherein at least four spatially continuous fixed catalyst layer zones exist in the reaction tube, the fixed catalyst layer zones have high activity in the direction from an inlet to an outlet of the reaction tube, and the fixed catalyst layer zones include first to fourth fixed catalyst layer zones, and
wherein a length (L) and an outer diameter (D) of the catalyst decreases from the first to the fourth fixed catalyst layer zones.

2. The method for producing unsaturated aldehydes and unsaturated carboxylic acids according to claim 1 , wherein, in the plurality of independent spaces inside the shell, heat transfer to the reaction tube is performed by the flow of an independent multi-stage heat medium having a high temperature in the direction from an inlet to an outlet of the reaction tube.

3. The method for producing unsaturated aldehydes and unsaturated carboxylic acids according to claim 1 , wherein
the plurality of the tube sheets separate the inside of the shell into two independent spaces,
two spaces separated by the plurality of tube sheets are divided into two spatially continuous zones by a baffle, and
four fixed catalyst layer zones corresponding to the zones formed by the baffle may exist in the reaction tube.

4. The method for producing unsaturated aldehydes and unsaturated carboxylic acids according to claim 3 , wherein the first to fourth fixed catalyst layer zones have high activity in the direction from an inlet to an outlet of the reaction tube, and the first fixed catalyst layer zone can have activity which is 75 to 85% of the catalytic activity of the fourth fixed catalyst layer zone.

5. The method for producing unsaturated aldehydes and unsaturated carboxylic acids according to claim 3 , wherein the inside of the shell is separated into first and second independent inner spaces in the direction from an inlet to an outlet of the reaction tube by the plurality of tube sheets, and the temperature of the first heat medium flowing through the first inner space is adjusted to be lower than the temperature of the second heat medium flowing through the second inner space.

6. The method for producing unsaturated aldehydes and unsaturated carboxylic acids according to claim 5 , wherein in the first inner space, heat transfer to the reaction tube is performed at a temperature of 295 to 350° C. by the flow of the first heat medium, and in the second inner space, heat transfer to the reaction tube is performed at a temperature of 300 to 400° C. by the flow of the second heat medium.

7. The method for producing unsaturated aldehydes and unsaturated carboxylic acids according to claim 1 , wherein the catalyst is a composite metal oxide represented by the following Chemical Formula 1,
Mo a Bi b M 1 c M 2 d M 3 e M 4 f M 5 g M 6 h O i   [Chemical Formula 1]

In Chemical Formula 1,
Mo is molybdenum,
Bi is bismuth,
M 1 is at least one element selected from the group consisting of W, Sb, As, P, Sn, and Pb,
M 2 is at least one element selected from the group consisting of Fe, Zn, Cr, Mn, Cu, Pd, Ag, and Ru,
M 3 is at least one element selected from the group consisting of Co, Cd, Ta, Pt, and Ni,
M 4 is at least one element selected from the group consisting of Al, Zr, V, and Ce,
M 5 is at least one element selected from the group consisting of Se, Ga, Ti, Ge, Rh, and Au,
M 6 is at least one element selected from the group consisting of Na, K, Li, Rb, Cs, Ca, Mg, Sr, and Ba, and
a, b, c, d, e, f, g, h and i are an atomic ratio of respective elements,
wherein a=12, b is in a range of 0.01 to 20, c is in a range of 0 to 20, d is in a range of 0.001 to 15, e is in a range of 0.001 to 20, f is in a range of 0 to 20, g is in a range of 0 to 10, h is in a range of 0.001 to 10, and i is a numerical value that is determined by the state of oxidation of the respective elements.

Assignees

• Lg Chemical Ltd

Inventors

• Choi Byung Yul
• Shin Hyun Jong
• Chang Junghoon
• Choe Young Hyun
• Ko Jun Seok
• Jeon Sang Hun

Classifications

• B01J2208/00221

  comprising baffles for guiding the flow of the heat exchange medium · CPC title

• B01J2208/00238

  Adjusting the heat-exchange profile by adapting catalyst tubes or the distribution thereof, e.g. by using inserts in some of the tubes or adding external fins · CPC title

• B01J2208/021

  comprising a plurality of beds with flow of reactants in parallel · CPC title

• C07C45/35

  in propene or isobutene · CPC title

• C07C51/252 Primary

  of propene, butenes, acrolein or methacrolein · CPC title