http://www.owlnet.rice.edu/~ceng403/gr21099/acrylicacid2.

htm

details in other doc

http://www.google.co.in/patents/US3859175

The boiling point of acetic acid is 118C, and it is difficult to remove acetic acid from a mixture of
acrylic acid and acetic acid by the ordinary distillation.

To overcome this problem of the separation of acetic acid from acrylic acid containing acetic
acid, it has been proposed to use a suitable entrainer and azeotropically distill off acetic acid. It
is known that toluene, methylcyclohexanone, n-heptane, diisobutylene, etc. are effective as the
entrainer. Indeed, acetic acid can be removed by an azeothropic distillation, but a considerably
larger amount of the entrainer must be separated from acrylic acid than that of acetic acid
contained in crude acrylic acid. The boiling points of these entrainers usually ranges from 100 to
110C, and the entrainers are not always easy to separate from acrylic acid. Furthermore, acrylic
acid is also transferred into the entrainer obtained by azeotropically distilling acetic acid at the
top of a distillation column, in addition to acetic acid, and therefore acrylic acid must be
separated from an azeotropic mixture containing same and recovered. Loss of acrylic acid will
be larger, if the acrylic acid is not recovered from the distillate entrainer. Therefore, in the known
process for separating acetic acid from acrylic acid by azeotropic distillation there are involved
very difficult and troublesome operations. Therefore, the known process is not advantageous
from the viewpoint of economy and operation.

http://www.google.co.in/patents/US4166774

capital cost reduction and energy savings may be obtained in the process for the recovery of
acrylic acid from an aqueous solution containing 10-80% acrylic acid resulting from the oxidation
of propylene or acrolein wherein the acrylic acid and acetic acid is extracted with a solvent
boiling below the boiling point of acrylic acid, the extractant containing solvent, acrylic acid,
acetic acid and water is distilled in a solvent recovery column to obtain an overhead stream of
solvent and water, and a bottoms stream of acrylic acid, the improvement comprising removing
a vapor stream from below the feed tray of the solvent recovery column and rectifying said
vapor stream to remove acetic acid.

https://www.google.com/patents/US3830707

an azeotropic distillation mixture with acetic acid for separating acrylic acid from a mixture
containing acrylic acid and acetic acid as mentioned above by employing azeotropic distillation
and it has been found that isooctane and nitroethane have excellent properties as such
azeotropic agents.

https://www.google.com/patents/US3433831
it has now been found that acetic acid can readily be separated from acrylic acid by distillation
when an entrainer capable of forming an azeotropic mixture with acetic acid is present. The
entrainer comprises two groups of components. The first group of components includes aliphatic
or alicyclic hydrocarbons having 7 carbon atoms or toluene or a mixture thereof. The second
group of components includes water, esters of the chemical formula R COOR wherein R is a
hydrocarbon radical having 1-3 carbons and R is a hydrocarbon radical having 14 carbons,
whose boiling point does not exceed C., nitriles having from 2 to 4 carbon atoms, and any
mixtures thereof. The first component alone may be used but the effect can be further increased
by the addition of the second component.

When the first component only is used as an entrainer in the azeotropic distillation, the first
component forms an azeotropic mixture with acrylic acid even though in a small amount.
Accordingly, a part of the acrylic acid will necessarily be distilled out when distilling acetic acid.
However, when the second component is added to the first component, substantially no acrylic
acid enters the acetic acid distillate. The mixing ratio of the first component to the second
component is 1 mol of the former to 0.05-1.5 moles of the latter, preferably 0.2-1.5.

For acrylic acid water mixture:

http://www.freepatentsonline.com/5154800.html

For catalyst type:

http://pubs.acs.org/doi/pdf/10.1021/i360035a012

For acetic acid water mixture

https://www.google.com/patents/US5160412

Acetic acid is difficult to separate from water by conventional distillation or rectification because
of the close proximity of their boiling points. Acetic acid can be readily separated from water by
using azeotropic distillation. Typical examples of effective agents are ethyl n-valerate and 4-
methyl-2-pentanone.

http://folk.ntnu.no/skoge/prost/proceedings/adconip-2014/pdf/SUBS21TO40/0032/0032_FI.pdf

Acetic acid is the most widely used aliphatic carbonic acid used as a reaction partner during the
manufacture of acetic acid esters, or employed as a solvent in the production of cellulose acetate.
Although acetic acid and water do not form any azeotrope, use of simple distillation to separate these
two components is still not practical due to its high energy consumption rate. In this work, some
separation designs that with high potential for energy saving for dehydration of acetic acid, such as
multi-effect distillation, azeotropic distillation, and liquid-liquid extraction, etc., are investigated and
analyzed in detail. It shows that the liquid-liquid extraction with methyl tert-butyl ether (MTBE) as
extraction agent is the most promising separation method in this system due to its lower energy
consumption and the total annual cost (TAC).