Process for preparing acrylic acid using an alkali metal-free and alkaline earth metal-free zeolitic material

Patent metadata

Field	Value
Publication number	US-9540305-B2
Application number	US-201514724244-A
Country	US
Kind code	B2
Filing date	May 28, 2015
Priority date	May 30, 2014
Publication date	Jan 10, 2017
Grant date	Jan 10, 2017

Abstract

A process for preparing acrylic acid, comprising (i) providing a stream S4 comprising a formaldehyde source and acetic acid; (ii) contacting stream S4 with an aldol condensation catalyst comprising a zeolitic material comprising aluminum in the framework structure to obtain a stream S6 comprising acrylic acid, the framework structure of the zeolitic material in (ii) comprising YO 2 and Al 2 O 3 , and Y being a tetravalent element; where the total content of alkali metal and alkaline earth metal in the zeolitic material in (ii), calculated as alkali metal oxide and alkaline earth metal oxide, is from 0% to 0.1% by weight, based in each case on the total weight of the zeolitic material, and where the aldol condensation catalyst in (ii) comprises, outside the framework structure of the zeolitic material present therein, from 0% to 1% by weight of vanadium, based on vanadium as vanadium(V) oxide.

First claim

The invention claimed is:

1. A process for preparing acrylic acid, the process comprising
contacting a stream comprising a formaldehyde source and acetic acid with an aldol condensation catalyst comprising a zeolitic material having a framework structure comprising aluminum to obtain a stream comprising acrylic acid,
wherein
the framework structure of the zeolitic material comprises YO 2 , X 2 O 3 and Al 2 O 3 ,
wherein Y is a tetravalent element; and
X is a trivalent element other than aluminum,
a total content of alkali metal and alkaline earth metal in the zeolitic material calculated as alkali metal oxide (M 2 O) and alkaline earth metal oxide (MO), is from 0% to 0.1% by weight, based on a total weight of the zeolitic material, and
the aldol condensation catalyst further comprises from 0% to 1% by weight of vanadium, calculated as vanadium(V) oxide and based on a total weight of the aldol condensation catalyst.

2. The process according to claim 1 , wherein the zeolitic material is a silicoaluminophosphate (SAPO) material or an aluminophosphate (APO) material.

3. The process according to claim 1 , wherein Y is at least one tetravalent element selected from the group consisting of Si, Sn, Ti, Zr, Ge, and V.

4. The process according to claim 1 , wherein X is at least one trivalent element selected from the group consisting of B, In, Ga, a transition metal of groups 3 to 12.

5. The process according to claim 1 , wherein the zeolitic material is at least partly in an H form.

6. The process according to claim 5 , wherein
a molar NH 4 + :(Al+X) ratio of the zeolitic material, when the zeolitic material is saturated with NH 3 , is from 0.01:1 to 1:1.

7. The process according to claim 1 , wherein the zeolitic material comprises at least one non-framework element Z selected from the group consisting of Ti, Zr, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Zn, Ga, Ge, In, Sn, Pb, P, N, and S and any combination thereof.

8. The process according to claim 7 , wherein the at least one non-framework element Z is selected from the group consisting of N, P and S, wherein the at least one non-framework element is present at least partly in an oxidic form.

9. The process according to claim 1 , wherein the zeolitic material has a structure selected from the group consisting of BEA, MFI, MWW, FAU, MEL, MTN, RRO, CDO LTL, MOR, AFI, FER, LEV and any combination thereof.

10. The process according to claim 1 , wherein the aldol condensation catalyst further comprises a binder material.

11. The process according to claim 1 , wherein the aldol condensation catalyst is in a form of shaped bodies, is in a star shape, is in a tablet form, is in a form of spheres, or is in a form of hollow cylinders.

12. The process according to claim 1 , wherein the contacting is effected at a temperature of from 200 to 400° C.

13. The process according to claim 1 , wherein
a space-time yield in the contacting is from 0.01 to 2.5 kg/kg/h, and
the space-time yield is defined as kg(acrylic acid)/kg(aldol condensation catalyst)/h.

14. The process according to claim 1 , wherein the formaldehyde source is an anhydrous formaldehyde source.

15. The process according to claim 1 , wherein
a temperature-programmed desorption with NH 3 (NH 3 -TPD) of the zeolitic material has a desorption spectrum with a desorption maximum within at least one of temperature ranges of from 0 to 250° C., from 251 to 500° C., or from 501 to 700° C., and
following deconvolution of the desorption spectrum, the desorption maximum in the temperature range of 0 to 250° C. has a concentration of desorbed NH 3 in a range of from 0.05 to 2.0 mmol/g, the desorption maximum in the temperature range of 251 to 500° C. has a concentration of desorbed NH 3 in a range of from 0.05 to 1.5 mmol/g, and the desorption maximum in the temperature range of 501 to 700° C. has a concentration of desorbed NH 3 in a range of from 0.001 to 0.5 mmol/g, wherein the concentration of desorbed NH 3 is defined as mmol(desorbed NH 3 )/g(zeolitic material).

Assignees

• Basf Se

Inventors

• Parvulescu Andrei-Nicolae
• Lange De Oliveira Armin
• Schunk Stephan A
• Woerz Nicolai Tonio
• Hartmann Marco
• Amakawa Kazuhiko
• Goebel Michael
• Liu Yong
• Lejkowski Michael

Classifications

• C07C51/353 Primary

  by isomerisation; by change of size of the carbon skeleton · CPC title

• B01J29/85

  Silicoaluminophosphates [SAPO compounds] · CPC title

• C07C2529/83

  Aluminophosphates (APO compounds) · CPC title

• C07C2529/82

  Phosphates · CPC title

• C07C2529/85

  Silicoaluminophosphates (SAPO compounds) · CPC title