EP1802564A1

EP1802564A1 - Use of phosphoric esters as deposit control agents during the synthesis, purification or regeneration of (meth)acrylic monomers

Info

Publication number: EP1802564A1
Application number: EP05809243A
Authority: EP
Inventors: Jean-François Croizy; Michel Fauconet; Jean-Michel Paul; René BONNAZ
Original assignee: Arkema France SA
Current assignee: Arkema France SA
Priority date: 2004-10-11
Filing date: 2005-10-07
Publication date: 2007-07-04
Also published as: US20090203938A1; FR2876374B1; FR2876374A1; WO2006040457A1

Abstract

The compounds of formula (I) are suggested for use as deposit control agents preventing the deposit of polymeric compounds or resulting in addition reactions on the (meth)acrylic double bonds during synthesis, purification, or regeneration of (meth)acrylic monomers operations. R1 represents a C3-C30 alkyl radical, an aryl radical or an alkylaryl radical, these radicals being able to be interrupted or bound to the oxygen of the molecule by a chain -(OR4)o- or the R4's, independent of one another, represent an ethylene, propylene or butylene chain and, o is an integer from 1 to 50; R2 represents R1, a hydrogen atom or a counterion, and; R3 represents a hydrogen atom or a counterion.

Description

USE OF PHOSPHORIC ESTERS AS ANTI-DEPOSITION AGENTS DURING THE SYNTHESIS, PURIFICATION OR REGENERATION OF

MONOMERS (METH) ACRYLIC.

The present invention belongs to the field of synthesis, purification and regeneration of (meth) acrylic monomers such as acrylic acid and methacrylic acid as well as C 1 -C 6 alkyl acrylates and methacrylates. More particularly, the present invention relates to the suppression or at least to the limitation of the fouling phenomena due to the deposition of polymers and / or insoluble heavy products, in the installations used for the aforementioned operations of synthesis, purification or regeneration.

Synthetic reactions of the (meth) acrylic monomers include: catalytic gas phase oxidation of propylene or propane to produce acrylic acid; catalytic oxidation of isobutene or tertiobutanol to generate methacrylic acid; the synthesis of sulfuric methacrylamide from acetone cyanohydrin, methanol and sulfuric acid to produce methyl methacrylate; the production of (meth) acrylic esters from (meth) acrylic acid and alcohols.

It is indeed well known that one of the delicate points in the manufacture of (meth) acrylic monomers stems from the fact that these compounds are relatively unstable and evolve easily towards the formation of polymers. This evolution, caused by a radical reaction favored by the effect of temperature, is therefore particularly easy in the steps of synthesis and purification of these monomers, for example during distillation operations. The usual consequence of this process is the deposit in the equipment of the plant, solid polymers that eventually cause clogging and make it necessary to stop the workshop for cleaning, which is difficult and expensive in non-productive downtime.

To reduce these disadvantages, polymerization inhibitors are added to the streams. The polymerization inhibitors conventionally used in processes for purifying (meth) acrylic monomers are numerous. Mention may be made, among them, of phenolic compounds, phenothiazine and its derivatives, manganese salts, thiocarbamates and dithiocarbamates, N-oxyl compounds, amine compounds and nitroso compounds, examples of these various compounds being indicated more far.

The vast majority of the polymerization inhibitors are heavier compounds than the (meth) acrylic monomers to be purified. In the distillation stages, given their low volatility, they are only very slightly entrained in the vapor phases in equilibrium with the liquid phases of the rectification trays and can not therefore perform their role of protecting the monomer against polymerization in the upper parts of the columns. For this reason, these inhibitors are generally introduced at the head of columns, condensers, etc. which can be the seat of a liquid-vapor equilibrium leading to the condensation of flows rich in (meth) acrylic monomer.

The effectiveness of these polymerization inhibitors, used alone or in combination, is generally increased when they are used in combination with a introduction of oxygen or a gas stream containing oxygen at the bottom of the column. These polymerization inhibitors can be introduced as they are, for example when they are liquid, or in solution in a solvent and, preferably, in solution in the monomer itself.

Despite the use of polymerization inhibitors, the monomer purification operations are often accompanied by the formation of polymers, soluble or insoluble in the medium, depending on the nature of the monomer and the composition of the medium. In the most troublesome cases, the polymer formed is insoluble in the medium and precipitates in the form of a solid deposit.

Precipitation of the polymer in the medium occurs especially when the length of the polymer chain is sufficient or when multifunctional compounds generate bridges between certain units of the polymer, by a process known as crosslinking.

Another source of fouling of the solid deposition facilities is the presence of heavy compounds generated during the monomer synthesis reaction step.

For example, the manufacture of (meth) acrylic monomers is accompanied by the formation of compounds resulting from a Michael addition reaction of a molecule containing a labile hydrogen atom on the double bond of a compound ( meth) acrylic:

R ¹ R ¹

I I

RO-H + H ₂ C = CH-CO- [CH ₂ -CH-CO] _n -R "

II II ^Jn

O O

R ¹ R ¹

I I

RO-CH ₂ -CH-CO- [CH ₂ -CH-CO] _n -R "

II II ^Jn

OO with:

R = H, C ₁ -C ₈ alkyl, CH ₃ -C (O) O - R '= H, methyl R "= H, C ₁ -C ₈ alkyl n> 0

These addition compounds, depending on the medium which contains them and their molar masses (proportional to the number of n units) may be insoluble in this medium.

The formation of insoluble polymers or heavy compounds can occur rapidly at the point where the polymerization process or the Michael addition reaction is initiated, if the polymer or heavy compound is insoluble in the medium, or if produce during a purification process step in which these products, previously dissolved, become insoluble by modifying the composition of the original medium, for example during a concentration operation of the heavy compounds by separation of light, or during the elimination of a polar component responsible for their solubilization. For example, problems of polymer deposits frequently occur during the drying phases of the monomers. In conventional methods for recovering and purifying acrylic acid and methacrylic acid, which involve an absorption step in water (in the case of the manufacture of acrylic acid by oxidation of propylene or propane, or methacrylic acid by oxidation of isobutene or tertiary butyl alcohol), the monomers are found, in an intermediate stage, as a mixture in a medium rich in water (20 to 40% water). In the case of the production of methacrylic acid by hydrolysis of sulfuric methacrylamide, the crude methacrylic acid leaving this step contains 1 to 5% water. Water being a good solvent for chains Polymers poorly crosslinked, the polymers generated in the previous stages, solubilized in the initial medium, precipitate during the phase of removal of water (water title <0.5%), and are deposited in the boilers and funds of columns.

Troublesome deposition problems can also occur when trying to recover the maximum monomer (light compound) in a mixture rich in heavy compounds obtained at the bottom of the last columns of purification of the monomers. The enrichment of the medium with heavy compounds (polymers and addition derivatives) leads to the precipitation of solids which force to stop the installation for cleaning. To avoid reaching this stage, we are forced to limit the recovery rate of recoverable monomer, which causes a loss.

Similarly, the treatment of heavy residues distillation monomers, in order to recover light fractions recoverable by thermal and / or catalytic cracking, generates significant fouling phenomena very penalizing industrially, or even making the operation impossible in some case.

Patent documents EP 839 790, DE 19 851 984 and US Pat. No. 4,440,625 disclose the use of alkyl or arylsulfonic acid derivatives as anti-fouling agents ("antifoulants") for the purpose of dispersing polymers. acrylic or heavy addition derivatives formed during the synthesis or purification of (meth) acrylic monomers, DE 19 851 984 also envisaging the case of tailing or cracking of distillation residues of (meth) acrylic monomers. However, the tests carried out in dynamic mode with this known family of products by the applicant company did not give any results. satisfactory from the point of view of industrial application.

The Applicant Company has therefore sought to solve the problems of fouling due to the deposition of solids of polymeric origin or resulting from addition reactions on the (meth) acrylic double bonds, and has discovered a family of compounds soluble in the medium containing the (meth) acrylic monomer and having the property of avoiding or effectively limiting the aforementioned deposits in the equipment for synthesis, purification or regeneration of the (meth) acrylic monomer.

The present invention therefore firstly relates to the use of at least one compound of formula (I):

in which: R ¹ represents a C ₃ -C ₃₀ alkyl radical, an aryl radical or an alkylaryl radical, these radicals being able to be interrupted or connected to the oxygen of the molecule by a chain - (OR ⁴ ) _o - where R ⁴ each independently represents an ethylene, propylene or butylene chain and o is an integer of 1 to 50;

R ² represents R ¹ , a hydrogen atom or a counterion;

R ³ represents a hydrogen atom or a counter-ion, as an anti-deposit agent (which can also be designated as antifouling or antifouling or antifouling agent) avoiding the deposit of compounds of polymeric nature or resulting from reactions of addition to the (meth) acrylic double bonds in synthetic or purification or regeneration of (meth) acrylic monomers.

Compounds (I) have a dispersant property and are also known as dispersants in the following. The compounds of formula (I) are especially chosen from those in which R ¹ and R ² each independently represent the radical where p is an integer of 4 to 12, preferably 8 or 9, and q is an integer of 4 to 50, preferably 6 to 20; and R ³ represents a hydrogen atom or a counterion; and / or those in which R ¹ represents the radical

where r is an integer of 4 to 12, preferably 8 or 9, and s is an integer of 4 to 50, preferably 6 to 20; and R ² and R ³ each independently represent a hydrogen atom or a counterion.

As counter-ion falling within the definition of R ² and R ³ , mention may be made of those resulting from the neutralization of the OH function in the case where R ² and / or R ³ = H by the alkanolamines and the hydroxides of alkali metals or alkaline earth metal. As particular examples, mention may be made of N ⁺ (CH ₂ CH ₂ OH) ₃ , Na ⁺ and K ⁺ . The compound (s) (I) can be introduced as such into the medium containing the (meth) acrylic monomer. They may also be introduced into the medium containing the (meth) acrylic monomer dissolved in a solvent, said solvent being chosen in particular from aromatic solvents, such as phthalates, such as diisononyl phthalate and dioctyl phthalate, and methyl glycols diethers. or in solution in the (meth) acrylic monomer. The compound (s) may be introduced at a concentration of from 0.01 to 1% by weight, especially from 0.05 to 0.5% by weight, into the medium containing the (meth) acrylic monomer to be prepared. purify or regenerate. The medium containing the (meth) acrylic monomer may also contain at least one polymerization inhibitor, in particular from 0.01% to 5% by weight, in particular from 0.05% to 3% by weight, relative to the medium containing the (meth) acrylic monomer to be prepared, purified or regenerated, the polymerization inhibitor (s) which can be chosen from: phenol derivatives such as hydroquinone and its derivatives such as methyl ether of hydroquinone; 2,6-di-tert-butyl-4-methyl phenol (BHT); and 2,4-dimethyl-6-tert-butyl phenol (Topanol A); phenothiazine and its derivatives such as methylene blue; manganese salts, such as manganese acetate; salts of thiocarbamic or dithiocarbamic acid, such as metal thiocarbamates and dithiocarbamates, such as copper di-n-butyldithiocarbamate; N-oxyl compounds, such as 4-hydroxy-2,2,6,6-tetramethyl piperidinoxyl; compounds with nitroso groups, such as N-nitroso phenyl hydroxylamine and its ammonium salts; quinones such as benzoquinone; amino compounds such as para-phenylenediamine derivatives, represented by the general formula (II):

wherein Z ¹ and Z ² each independently represent an alkyl, aryl, alkylaryl or arylalkyl radical, an example being N, N'-di-sec-butyl para-phenylenediamine.

The invention reduces solids deposition in monomer purification plants

(meth) acrylic, thus reducing the frequency of stops necessary for cleaning columns, exchangers, boilers, condensers, reactors ...

A second advantage may be to reduce the amount of stabilizers introduced into the purification equipment, to reduce their cost.

Recovery with better yields of noble products ^(monomers, reactants) in the concentrations, or thermal or catalytic cracking, is another advantage.

The operations concerned by the present invention are very diverse and include the following: reaction stages of acid synthesis or (meth) acrylic esters such as those listed in the preamble of the present description; purification steps of (meth) acrylic acids or esters, in particular during the distillation separation steps; reactive generation steps and reaction products by thermal cracking, batchwise or continuously, in the presence or absence of catalyst.

In the case of the use according to the invention, where the operation involves a distillation column, the compounds (I) are introduced preferentially at the top of the column.

The present invention will now be described using Examples, Reference Examples and Comparative Examples. In all these examples, the percentages are by weight, and the following abbreviations are used:

Stabilizers or polymerization inhibitors - PTZ: phenothiazine

PMP: paramethoxyphenol HQ: hydroquinone

Solvent - MIBK: Methyl Isobutyl Ketone

The dispersant used in the Examples of the invention is a mixture of neutralized ethoxylated alkylphenol mono- and diphosphate, as defined in formula (I) above, dissolved in an aromatic solvent.

Example 1 (of the invention)

A glass distillation equipment is used, comprising a distillation column, a boiler, a condenser and a reflux tank.

The column, with a diameter of 38 mm, is lined with a multiknit element made of 316L stainless steel with a height of 14 cm. The vapors are generated at the bottom in a thermosiphon boiler heated by electrical resistances, of volume 200 ml, into which acrylic acid stabilized with 0.2% PTZ and 0.2% PMP is introduced. A continuous flow of air is further ensured in the liquid of the boiler. The vapors are condensed at the top through a water-cooled condenser and collected in a reflux tank. The assembly is placed under reduced pressure of 1.6 x 10 ⁴ Pa

(120 mmHg), and the temperature measured in the foot is 89 ^° C.

The condensed liquid flow at the top is 540 g / h.

Continuous introduction of PMP and PTZ (10 ppm of each of the stabilizers, with respect to the distillate flow rate) and of the dispersant (0.3% relative to the distillate flow rate), in solution in acrylic acid, is carried out in this container.

The liquid collected in the reflux tank is returned by a pump at the top of the column, maintaining a constant level in this container. The liquid level in the boiler is kept constant by withdrawing the excess liquid.

After 3 hours of operation, the mass of polymer deposited in the multiknit packing is 6.5 g.

Reference Example 1

A reference Example is carried out under the same conditions as those of Example 1, but without the dispersant: the mass of polymer recovered in the packing is 25.1 g.

Example 2

In the same assembly as in Example 1, except for the packing of the column, this time consisting of a multiknit packing element of height 4 cm and Raschig rings made of glass, over a height of 11 cm, a mixture is introduced. of acrylic acid containing 5% water. An acrylic acid feed containing the PMP and PTZ stabilizers and the dispersant is provided so as to send at the top of the column, 10 ppm of each of the polymerization inhibitors and 0.1% of dispersant, relative to the measured distillate flow rate (740 g / h).

After 3 hours of operation, the mass of polymer deposited in the multiknit packing is 4 g.

Reference Example 2

A reference Example is carried out under the same conditions as those of Example 2, but without the dispersant: the mass of polymer recovered in the packing is 28 g.

Comparative Example 2

A Comparative Example is carried out under the same conditions as those of Example 2, but with pure acrylic acid and dodecylbenzene sulfonic acid as dispersant: the mass of polymer recovered in the packing is 15.9 g.

Example 3

In the assembly and conditions of Example 2, pure methacrylic acid is introduced, replacing acrylic acid.

No solid deposit was observed in the packing of the column.

After 3 hours of testing, in the presence of the dispersant (0.1% relative to the distillate flow), the liquid solution contained in the boiler is cloudy, with some fine solids in suspension. After draining the liquid, some solid particles remain attached to the wall of the boiler, and disappear by a simple washing with water.

Reference Example 3

Under the same conditions as in Example 3, but in the absence of the dispersant, the solid particles are agglomerated into a cluster partly suspended, and partly adhered to the wall. Deposits clinging to the wall, in greater quantity than Example 3 carried out with dispersant, are not removed by washing with water.

Examples 4a and 4b of the invention and reference Examples 4a and 4b

This example describes the application of the present invention to the recovery of noble products by thermal cracking, from a stream obtained at the bottom of the column for removing heavy compounds from a butyl acrylate manufacturing process. The mixture, composed of:

10.2% butyl acrylate; 69.6% butyl 2-butoxypropionate; 7.2% butyl 2-acryloxypropionate; 2.5% of butyl 2-hydroxypropionate;

3% of PTZ (the rest being composed of polymers and other heavy compounds in lower concentration), is valorized with the aim of recovering acrylic acid, butyl acrylate and butanol engaged in this mixture.

The recovery is done in two stages: elimination of the heavier compounds (in particular the polymers) in a vaporization step (Examples 4a of the invention and by reference), then cracking the vaporized fraction in the presence of acid ^sulfuric catalyst (Examples 4b of the invention and reference). • In the first step of the process (vaporization), a thermosiphon circulation glass boiler, heated by electrical resistors, with a volume of 90 ml, is fed at a rate of 360 g / h by the mixture of heavy. The boiler is equipped with a head section at the top, consisting of a glass element filled with a 3 cm high multiknit filling. The distilled stream at the top is condensed through a circulating exchanger with water, and collected in a receiver.

The operation is carried out under reduced pressure of 6.7 × 10 ³ Pa (50 mmHg) at a temperature of 146 ^° C., measured in the boiler. 189 g / h of a mixture composed of:

24.3% butyl acrylate;

66.3% butyl 2-butoxypropionate; - 3.8% of butyl 2-acryloxypropionate; 2.8% butyl 2-hydroxypropionate; 0.7% butanol.

In a first test (Reference Example 4a), the mixture is introduced without addition of dispersant. After 5 hours of operation, the wall of the boiler is completely covered with a solid deposit very difficult to eliminate, which makes this method of recovery unusable industrially. In a second test (Example 4a of the invention), 0.04% of the dispersant is added to the feed medium, and it is found that the wall of the boiler is clean after 10 hours of operation. • In the second step of the process (catalytic thermal cracking), the same assembly is used, the boiler having this time a function of cracking reactor. The vaporizer head stream recovered in the previous step is supplemented with sulfuric acid (4% in the medium) and PTZ (1.4%), and then introduced at a rate of 180 g / h, into the reactor .

The temperature imposed in the cracker is 186 ^° C., and 146 g / h of a mixture containing: 71.3% of butyl acrylate are condensed at the top;

1.1% butyl 2-butoxypropionate; 0.2% butyl 2-acryloxypropionate; 0.04% butyl 2-hydroxypropionate; 14.8% butanol and 2.5% water. In a first test (Reference Example 4b), the mixture is introduced without addition of dispersant. After 2 hours of operation, the reactor wall is covered with a solid deposit very difficult to remove.

In a second test (Example 4b_ of the invention), 0.12% of the dispersant is added to the feed medium, and it is found that the wall of the boiler is clean after 6 hours of operation.

Claims

1 - Use of at least one compound of formula (I):

in which: R ¹ represents a C ₃ -C ₃₀ alkyl radical, an aryl radical or an alkylaryl radical, these radicals being able to be interrupted or connected to the oxygen of the molecule by a chain - (OR ⁴ ) _o -, wherein each R ⁴ is independently an ethylene, propylene or butylene chain and o is an integer of 1 to 50;

R ² represents R ¹ , a hydrogen atom or a counterion;

R ³ represents a hydrogen atom or a counter-ion, as anti-deposit agent avoiding the deposition of compounds of a polymeric nature or resulting from addition reactions on the (meth) acrylic double bonds during the synthesis or purification operations or regeneration of (meth) acrylic monomers.

2 - Use according to claim 1, characterized in that the compounds of formula (I) are chosen from those in which R ¹ and R ² each independently represent the radical C _p H _{2p + 1} - (Q / - ( ^OCH ₂ CH ₂ ) _q -

where p is an integer of 4 to 12, preferably 8 or 9, and q is an integer of 4 to 50, preferably 6 to 20; and R ³ represents a hydrogen atom or a counterion; and / or those in which R ¹ represents the radical

3 - Use according to one of claims 1 and 2, characterized in that the compound (s) (I) are introduced as such in the medium containing the monomer (meth) acrylic.

4 - Use according to one of claims 1 and 2, characterized in that the compound (s) (I) are introduced into the medium containing the (meth) acrylic monomer in solution in a solvent or in solution in the monomer ( meth) acrylic acid.

5 - Use according to claim 4, characterized in that the solvent is chosen from aromatic solvents such as phthalates, such as diisononylphthalate and dioctylphthalate, and methyl diethers of glycols.

6 - Use according to one of claims 1 to 5, characterized in that the compound (s) (I) are introduced at a concentration of 0.01% to 1% by weight in the medium containing the monomer (meth) acrylic to prepare, purify or regenerate.

7 - Use according to claim 6, characterized in that the compound (s) (I) are introduced at a concentration of 0.05 to 0.5% by weight in the medium containing the (meth) acrylic monomer to be prepared, purify or regenerate.

8 - Use according to one of claims 1 to 7, characterized in that the medium containing the (meth) acrylic monomer contains at least one polymerization inhibitor, in particular from 0.01% to 5% by weight, in particular from 0.05% to 3% by weight, relative to medium containing the (meth) acrylic monomer to be prepared, purified or regenerated.

9 - Use according to claim 8, characterized in that the polymerization inhibitor or inhibitors are chosen from: phenol derivatives such as hydroquinone and its derivatives such as methyl ether hydroquinone; 2,6-ditertbutyl-4-methyl phenol; and 2,4-dimethyl-6-tert-butyl phenol; phenothiazine and its derivatives such as methylene blue; manganese salts, such as manganese acetate; salts of thiocarbamic or dithiocarbamic acid, such as metal thiocarbamates and dithiocarbamates such as copper di-n-butyldithiocarbamate; N-oxyl compounds, such as 4-hydroxy-2,2,6,6-tetramethyl piperidinoxyl; compounds with nitroso groups, such as N-nitroso phenyl hydroxylamine and its ammonium salts; quinones such as benzoquinone; amino compounds such as para-phenylenediamine derivatives, represented by the general formula (II):

wherein Z ¹ and Z ² each independently represent an alkyl, aryl, alkylaryl or arylalkyl radical. 10 - Use according to one of claims 1 to 9, characterized in that the operations concerned are: the reaction stages of synthesis of (meth) acrylic acids or esters, such as catalytic gas phase oxidation of propylene or propane to make acrylic acid; catalytic oxidation of isobutene or tertiobutanol to generate methacrylic acid; the synthesis of sulfuric methacrylamide from acetone cyanohydrin, methanol and sulfuric acid to produce methyl methacrylate; the production of (meth) acrylic esters from (meth) acrylic acid and alcohols; the steps of purification of (meth) acrylic acids or esters, in particular during the steps of separation by distillation; and the steps of generating reactants and reaction products by thermal cracking, batchwise or continuously, in the presence or absence of catalyst.

11 - Use according to one of claims 1 to

10, wherein the operation involves a distillation column, characterized in that the compounds (I) are introduced preferentially at the top of the column.

12 - Use according to one of claims 1 to

11, characterized in that the (meth) acrylic monomers are chosen from acrylic acid and methacrylic acid as well as C ₁ -C ₈ alkyl acrylates and methacrylates.