阅读说明：本技术 具有硫酸处理的安赛蜜的制备方法 (Preparation method of acesulfame with sulfuric acid treatment ) 是由 汉斯·沃尔夫冈·埃贝茨 于 2018-01-18 设计创作，主要内容包括：本发明总体上涉及一种制备产物的方法,所述产物为6-甲基-3,4-二氢1,2,3-恶噻嗪-4-酮2,2-二氧化物或其衍生物。本发明还涉及这种方法在制备硫酸二铵中的应用。本发明涉及一种制备产物的方法,所述产物为6-甲基-3,4-二氢1,2,3-恶噻嗪-4-酮2,2-二氧化物或其衍生物,所述方法包括以下步骤：a.使SO<Sub>3</Sub>与乙酰乙酰胺-N-磺酸或其衍生物在胺的存在下接触,从而获得包含胺和硫酸的第一物流；b.提供包含氨的第二物流；c.提供回路；d.在A点处将所述第二物流引入所述回路,在B点处将所述第一物流引入所述回路,以获得在所述回路中循环的循环流；e.在C点处去除一部分所述循环流以获得第三物流；其中循环比为3至30；根据以下-20公式,所述循环比为紧接在A点之前的循环流的质量流量的值Fc除以在B点处引入所述回路的第一物流的质量流量的值F：循环比＝Fc/F2图130。(The present invention generally relates to a process for preparing a product which is 6-methyl-3, 4-dihydro-1, 2, 3-oxathiazin-4-one 2, 2-dioxide or a derivative thereof. The invention also relates to the use of this process for the preparation of diammonium sulphate. The present invention relates to a process for preparing a product which is 6-methyl-3, 4-dihydro-1, 2, 3-oxathiazin-4-one 2, 2-dioxide or a derivative thereof, comprising the steps of: a. make SO 3 With acetoacetamide-N-sulfonic acid or a derivative thereof in the presence of an amine, thereby obtaining a first stream comprising the amine and sulfuric acid; b. providing a second stream comprising ammonia; c. providing a loop; d. introducing said second stream into said circuit at point a and said first stream into said circuit at point B to obtain a recycle stream that is recycled in said circuit; e. removing a portion of the recycle stream at point C to obtain a third stream; wherein the recycle ratio is from 3 to 30; the circulation ratio is the value of the mass flow of the circulation flow immediately before point A, Fc divided by the introduction of the recirculation at point B, according to the following equation-20Value F of the mass flow of the first stream of the circuit: cycle ratio Fc/F2 fig. 130.)

1. A process for preparing a product which is 6-methyl-3, 4-dihydro-1, 2, 3-oxathiazin-4-one 2, 2-dioxide or a derivative thereof, comprising the steps of:

a. make SO₃With acetoacetamide-N-sulfonic acid or a derivative thereof in the presence of an amine, thereby obtaining a first stream comprising the amine and sulfuric acid;

b. providing a second stream comprising ammonia;

c. providing a loop;

d. introducing said second stream into said circuit at point a and said first stream into said circuit at point B to obtain a recycle stream that is recycled in said circuit;

e. removing a portion of the recycle stream at point C to obtain a third stream;

wherein the recycle ratio is from 3 to 30; the recycle ratio is the value of the mass flow of the recycle stream immediately before point a, Fc, divided by the value of the mass flow of the first stream introduced into the loop at point B, F1, according to the following formula:

the cycle ratio is Fc/F1.

2. The method of claim 1, wherein the amine is triethylamine.

3. The method of claim 1 or 2, wherein the third stream is removed from the recycle stream at point C, and the A, B and point C are ordered in the loop in the flow direction of the recycle stream.

4. The method of any of the preceding claims, wherein the second stream comprises no more than 50 wt% H₂O。

5. The method of any one of the preceding claims, wherein the second stream is a liquid.

6. The process according to any one of the preceding claims, wherein the pressure of the second stream is from 0.2 to 1.5 MPa.

7. The method according to any one of the preceding claims, further comprising the step of:

f. separating the third stream to obtain a fourth stream comprising amines and a fifth stream comprising diammonium sulfate;

wherein the fourth stream comprises a higher wt% amine than the first stream;

wherein the fourth stream comprises a lower wt% diammonium sulfate than the first stream.

8. The method of claim 7Process in which in step g₁With H₂And (4) contacting with O.

9. The method of claim 8, wherein in step g₁At least part of H₂O, preferably all H₂O exists in a gaseous state.

10. The process of any of claims 7-9, wherein the mass ratio of the fourth stream to the fifth stream is from 30:70 to 1: 99.

11. The method according to any one of claims 7-10, wherein in step g₂Reducing H in the fifth stream₂And (4) the content of O.

12. The method of claim 11, wherein said step g is performed₂Is cured.

13. The process according to any one of claims 7-12, wherein the fourth stream is separated into a sixth stream and a seventh stream in step h.

Wherein the seventh stream comprises more H than the sixth stream₂O；

Wherein the sixth stream comprises more amine than the seventh stream.

14. The process of claim 13, wherein step h is distillation.

15. The method of any one of the preceding claims, wherein the recycle stream is heated or cooled.

16. Use of a process according to any one of the preceding claims for the preparation of diammonium sulphate.

Technical Field

The present invention generally relates to a process for preparing a product which is 6-methyl-3, 4-dihydro-1, 2, 3-oxathiazin-4-one 2, 2-dioxide or a derivative thereof. The invention also relates to the use of this process for the preparation of diammonium sulphate.

Background

Acesulfame k and its derivatives are of great importance as sweeteners in food and medicine. Of particular interest are the non-toxic salts, the most notable of which is the potassium salt acesulfame potassium. Acesulfame potassium is commonly available under the trade name acesulfame potassium

And

sold and designated in the european union as E number E950. In view of the great demand for acesulfame k as a sweetener, about twenty thousand metric tons per year in the world, there is an urgent need for improvement of the production process thereof, which can save a large amount of money economically and ecologically even with a slight improvement of the production process.

An early approach to acesulfame k production was to use halogen-based intermediates. Examples are given in Angewandte Chemie 85, No.22(1973), pages 965 to 73, corresponding to the International edition Vol.12, No.11(1973), pages 869-76. The majority of the processes therein start with chlorosulfonyl or fluorosulfonyl isocyanates. Another example is given in german patent publication No.2,453,063, which discloses a process starting from sulphamoyl fluoride.

The process for the preparation of acesulfame k via acetoacetamide-N-sulfonic acid may provide advantages starting from more readily available starting materials. An example of such a method is presented in chinese patent application 201310531442.

European patent document EP 2560919B 2 describes a process for the preparation of diammonium sulfate.

However, there is still a need for improved processes for the preparation of acesulfame, in particular for the removal of sulphuric acid.

Disclosure of Invention

In general, it is an object of the present invention to at least partly overcome the disadvantages arising from the prior art.

The object of the present invention is to provide a process for the preparation of acesulfame k or derivatives thereof with reduced energy consumption.

It is an object of the present invention to provide a process for the preparation of acesulfame k or derivatives thereof, wherein the conversion of spent sulfuric acid to diammonium sulfate has a reduced energy consumption.

It is an object of the present invention to provide a process for the preparation of acesulfame k or derivatives thereof with reduced energy consumption in two or more process steps.

The object of the present invention is to provide a method for preparing acesulfame k or derivatives thereof which have less influence on the environment.

Drawings

Fig. 1 is a schematic diagram illustrating the flow of material in a method according to the invention. A first stream 102 of liquid ammonia and a second stream 101 of a first stream 102 of acesulfame k preparation process comprising triethylamine, sulphuric acid and water, as well as other trace components, are introduced into the circuit to obtain a recycle stream, the first stream at point B in the circuit and the second stream at point a in the circuit. The recycle stream is cooled or heated in heat exchanger 103 and passed to phase separator 104 at point C in the loop. In phase separator 104, a portion of the recycle stream, referred to as the third stream, is separated to form diammonium sulfate and H₂A liquid fifth stream of O and comprising triethylamine and H₂A gaseous fourth stream of O. A portion of the fifth stream is recycled to the recycle stream, in this case 8 to 15 times that of the first stream. A part of the fifth stream leaving the circuit is continuously contacted with steam 105 to obtain an aqueous diammonium sulphate solution, which is subjected to a further treatment 106, and the steam part is brought into contact with the second streamAnd combining the four streams. Further processing of the fifth stream includes solidification to obtain solid diammonium sulfate. The fourth stream is distilled 107 together with added vapour components to triethylamine 108, which can be reused in the preparation of acesulfame k, and the water fraction 109 is recycled back to the first stream 102.

FIG. 2 is a schematic process flow diagram showing the steps of the present invention. SO in step a 201₃And acetoacetamide-N-sulfonic acid to form acesulfame k. This step produces a product containing H₂A first stream of O, triethylamine and sulfuric acid. A second stream of liquid ammonia is provided in step b 202. A loop is provided at step c 203. In step d 204, the first and second streams are introduced into the loop to obtain a recycle stream. The third stream is removed from the loop in step e 205. In separation step f, the third stream may be separated to comprise triethylamine and H₂A volatile fourth stream of O and comprising H₂A liquid fifth stream of O and diammonium sulfate. May then be carried out in step g ₁206 the fifth stream is combined with H in vapour form₂O and in step g₂The resulting diammonium sulfate is solidified in 207. The fourth stream may be distilled in step H208 for separation into a triethylamine phase and H₂And (4) an O phase. Purified triethylamine leaves the distillation column at the bottom.

Fig. 3 further illustrates the effect of water content in the diammonium sulfate (DASA) solution (flow to solidification 106). The power requirement for drying is affected by the water content. The power consumption was measured over the course of one hour.

Figure 4 shows the effect of varying the recycle ratio on the proportional conversion of sulfuric acid to diammonium sulfate, as well as the reynolds number and energy consumption of the pump. The parameters were measured over the course of one hour.

Detailed Description

Throughout this document, the hydrolysis step is also referred to as being with H₂And O contact.

6-methyl-3, 4-dihydro-1, 2, 3-oxathiazin-4-one 2, 2-dioxide is also known as acesulfame k, which is used in this document as a synonym for 6-methyl-3, 4-dihydro-1, 2, 3-oxathiazin-4-one 2, 2-dioxide.

The claims contribute to achieving at least one of the above objects. A contribution to achieving at least one of the above objects is made by the following embodiments, the numbering of which is indicated between the vertical bars.

L 1| a process for preparing a product which is 6-methyl-3, 4-dihydro-1, 2, 3-oxathiazin-4-one 2, 2-dioxide or a derivative thereof, comprising the steps of:

a. make SO₃With acetoacetamide-N-sulfonic acid or a derivative thereof in the presence of an amine, thereby obtaining a first stream comprising the amine and sulfuric acid;

b. providing a second stream comprising ammonia;

c. providing a loop;

d. introducing said second stream into said circuit at point a and said first stream into said circuit at point B to obtain a recycle stream that is recycled in said circuit;

e. removing a portion of the recycle stream at point C to obtain a third stream;

wherein the recycle ratio is from 3 to 30, preferably from 4 to 20, more preferably from 5 to 15, more preferably from 6 to 12, more preferably from 8 to 10; the recycle ratio is the value of the mass flow of the recycle stream immediately before point a, Fc, divided by the value of the mass flow of the first stream introduced into the loop at point B, F1, according to the following formula:

the cycle ratio is Fc/F1.

In one aspect of this embodiment, the first stream satisfies one or more of the following conditions:

i.) the content of sulfuric acid is from 35 to 75 wt.%, preferably from 45 to 65 wt.%, most preferably from 50 to 60 wt.%;

ii) the amine content is from 5 to 25 wt.%, preferably from 8 to 20 wt.%, most preferably from 10 to 15 wt.%.

iii.)H₂The content of O is 10 to 60 wt%, preferably 20 to 50 wt%, most preferably 25 to 40 wt%.

iv) the first stream comprises not more than 1 wt% of dichloromethane, preferably not more than 0.5 wt%, more preferably not more than 0.1 wt%, more preferably not more than 0.05 wt%.

In one aspect of this embodiment, the second stream satisfies one or more of the following conditions:

i.) the ammonia content is from 90 to 100 wt.%, preferably from 95 to 100 wt.%, most preferably from 99 to 100 wt.%;

ii.)H₂the content of O is 0 to 10 wt%, preferably 0 to 5 wt%, most preferably 0 to 1 wt%.

In one aspect of this embodiment, the third stream satisfies one or more of the following conditions:

i.)H₂the content of O is 10 to 45 wt%, preferably 15 to 35 wt%, most preferably 20 to 30 wt%;

ii) the content of diammonium sulphate is from 20 to 85 wt%, preferably from 25 to 75 wt%, most preferably from 40 to 70 wt%;

iii.) the amine content is from 5 to 30 wt.%, preferably from 10 to 25 wt.%, most preferably from 8 to 20 wt.%.

|2| the method of embodiment |1| wherein the amine is triethylamine.

L 3| the process according to embodiment |1| or |2| wherein the third stream is removed from the recycle stream at point C and the A, B and point C are ordered in the loop in the flow direction of the recycle stream.

The method of any of the preceding embodiments, wherein the second stream comprises no more than 50 wt% H₂O, preferably not more than 40 wt%, more preferably not more than 30 wt%, more preferably not more than 20 wt%, more preferably not more than 10 wt%, more preferably not more than 5 wt%, more preferably not more than 2 wt%, more preferably not more than 1 wt%. Most preferably, the second stream is free of H₂O。

The method of any one of the preceding embodiments, wherein the second stream is a liquid.

The process according to any of the preceding embodiments, wherein the pressure of the second stream is from 0.2 to 1.5MPa, preferably from 0.25 to 1.4MPa, more preferably from 0.3 to 1.3 MPa.

The method according to any of the preceding embodiments, further comprising the steps of:

f. separating the third stream to obtain a fourth stream comprising amines and a fifth stream comprising diammonium sulfate;

wherein the fourth stream comprises a higher wt% amine than the first stream;

wherein the fourth stream comprises a lower wt% diammonium sulfate than the first stream.

The separation step f is preferably a phase separation, preferably a volatile phase and a liquid. The fourth stream is preferably the volatile phase. The fifth stream is preferably a liquid. The preferred volatile phase is a gas. Preferably, the volatile phase is an azeotrope.

In one aspect of this embodiment, the fourth stream satisfies the following condition:

i.) the content of amine is from 60 to 95 wt.%, preferably from 65 to 90 wt.%, more preferably from 70 to 80 wt.%.

In one aspect of this embodiment, the fifth stream satisfies the following condition:

i.) the content of diammonium sulphate is from 30 to 85% by weight, preferably from 35 to 80% by weight, more preferably from 45 to 75% by weight.

I8I the method according to embodiment I7, wherein in step g₁With H₂And (4) contacting with O.

|9| the method according to embodiment |8| wherein in step g₁At least part of H₂O, preferably all H₂O exists in a gaseous state.

L 10| the method of any of embodiments |7| - |9| wherein the mass ratio of the fourth stream to the fifth stream is from 30:70 to 1:99, more preferably from 20:80 to 2:98, more preferably from 15:85 to 5: 95.

11| the method according to any of embodiments |7| - |10| wherein in step g₂Reducing H in the fifth stream₂And (4) the content of O. In one aspect of this embodiment, after step g2, some H₂O remains in the fifth stream. In another aspect of this embodiment, the H in the fifth stream is₂The O content is reduced to be substantially absent.

|12| the method according to embodiment |11| wherein the step g2 is curing. Preferred curing is one or more selected from the group consisting of: crystallization, precipitation and drying.

L 13| the method according to any of embodiments |7| - |12| wherein the fourth stream is separated into a sixth stream and a seventh stream in step h;

wherein the seventh stream comprises more H than the sixth stream₂O；

Wherein the sixth stream comprises more amine than the seventh stream.

|14| the method of embodiment |13| wherein the step h is distillation.

|15| the method according to any of the preceding embodiments, wherein the recycle stream is heated or cooled, preferably by a heat exchanger. The heat exchanger is preferably an active heat exchanger. The heat extracted from the recycle stream can be used to strip the sulfuric acid fed to the reaction as the first stream.

|16| use of a process according to any of the preceding embodiments in the preparation of diammonium sulfate.

Method of producing a composite material

At least one of the above objects is also achieved by a method for preparing a product which is 6-methyl-3, 4-dihydro-1, 2, 3-oxathiazin-4-one 2, 2-dioxide or a derivative thereof, comprising the steps of:

a. make SO₃With acetoacetamide-N-sulfonic acid or a derivative thereof in the presence of an amine, thereby obtaining a first stream comprising the amine and sulfuric acid;

b. providing a second stream comprising ammonia;

c. providing a loop;

d. introducing said second stream into said circuit at point a and said first stream into said circuit at point B to obtain a recycle stream that is recycled in said circuit;

e. removing a portion of the recycle stream at point C to obtain a third stream;

contacting step a and acesulfame K production

The contacting step a preferably produces acesulfame k.

In one embodiment, the contacting step a may constitute a series of chemical reactions, as shown in the following chemical equation I:

in other embodiments, the method may comprise a series of chemical reactions, similar to that shown in chemical equation I. In one aspect of this embodiment, a different CH is employed₂Cl₂The solvent of (3) is preferably one selected from the following solvent moieties. In one aspect of this embodiment, a base other than KOH is employed, and the resulting acesulfame k has a correspondingly different cation. In one aspect of this embodiment, an amine other than triethylamine is employed. In one aspect of this embodiment, equimolar is employedAmount of SO₃I.e. the parameter n is set to 1. Here, the formula (n-1) is equal to zero and H is not used₂O。

The process of the present invention preferably comprises a ring closure reaction wherein acetoacetamide-N-sulfonic acid or a derivative thereof reacts to form a ring. The closed loop is preferably formed by SO₃And (4) assisting.

In one embodiment of the method, the reacting with H is performed as part of step a₂And (c) the substep of O-contacting. And H₂The sub-step of O contacting is preferably for hydrolyzing the adduct, preferably containing SO₃The adduct of (1).

In one embodiment, the substep of neutralizing with a base is performed as part of step a. And preferably in the presence of H₂The substep of O-contacting is followed by one.

In a preferred embodiment, the contacting step a may be carried out at least partially in a reactor, preferably a tubular reactor. In one aspect of this embodiment, the contacting step a can be conducted at elevated pressure or elevated temperature or both. In one aspect of this embodiment, the first stream exits the reactor as a spray.

In one embodiment, the contacting step a is carried out at a temperature of from-70 to 175 ℃, preferably from 40 to 150 ℃, more preferably from 60 to 130 ℃, most preferably from 80 to 120 ℃.

In one embodiment, the contacting step a is carried out at a pressure of from 0.2 to 2MPa, preferably from 0.3 to 1.5MPa, more preferably from 0.4 to 1.2MPa, most preferably from 0.5 to 1 MPa.

In one embodiment, SO is used in step a₃The molar ratio to acetoacetamide-N-sulfonic acid or derivative thereof is from 1:1 to 20:1, preferably from 2:1 to 17:1, more preferably from 2.5:1 to 15:1, most preferably from 3:1 to 10: 1.

Said first stream is obtained from the contact product in step a by extracting acesulfame from sulfuric acid using a solvent, preferably using an extraction column. In one embodiment, acesulfame k is extracted from sulfuric acid using Dichloromethane (DCM). In one aspect of this embodiment, the DCM is at least partially removed to obtain the first stream.

In one embodiment, the step of contacting with a solvent is performed in the contacting step a, and if performed, preferably after the step of contacting with water. In this context, preferred solvents are inert solvents. The inert solvent preferably does not chemically react with the acetoacetamide-N-sulfonic acid or derivative thereof. The inert solvent preferably does not chemically react with the acesulfame k or derivatives thereof. The inert solvent is preferably at most mixed with SO₃Minimal reaction, based on SO₃Preferably, no more than 1 wt% SO is consumed in one hour₃. Preferred solvents for acetoacetamide-N-sulfonic acid or derivatives thereof are one or more selected from the group consisting of: halogenated aliphatic hydrocarbons, aliphatic sulfoxides and aliphatic sulfones. Preferred halogenated aliphatic hydrocarbons have up to four carbon atoms, preferably one or more selected from the group consisting of: dichloromethane, chloroform and 1, 2-dichloroethane. The preferred aliphatic sulfoxide is dimethyl sulfoxide. The preferred aliphatic sulfone is sulfolane. In one embodiment, the solvent for acetoacetamide-N-sulfonic acid or derivative thereof is one or more selected from the group consisting of: dichloromethane and 1, 2-dichloroethane, preferably dichloromethane.

In one embodiment, step a comprises the sub-step of at least partially removing the solvent, preferably dichloromethane, from the sulfuric acid. The solvent content in the sulfuric acid, preferably dichloromethane, is preferably reduced by heating.

The amine of step a may be a mono-, di-or trialkylamine, preferably a trialkylamine. Preferred trialkylamines are trimethylamine, triethylamine and tripropylamine, with triethylamine being preferred. Preferred monoalkylamines are monomethylamine, monoethylamine and monopropylamine, preferably monoethylamine. Preferred dialkylamines are dimethylamine, diethylamine and dipropylamine, preferably diethylamine. The preferred amine is triethylamine.

Hydrolysis

Step a may comprise a hydrolysis sub-step. The hydrolysis substep is preferably carried out by reacting the reaction product of step a with H₂And (c) the substep of O-contacting. Throughout this document, a hydrolysis substep may be referred to as a hydrolysis substep, and may also be referred to as a hydrolysis substep with H₂And (c) the substep of O-contacting. When step a is reversedThe product is an adduct, preferably with SO₃The hydrolysis substep is particularly preferred for the adducts of (a). In case the hydrolysis is carried out, preferably a separator step is also carried out to remove the hydrolysis products, preferably sulphuric acid.

And H₂The sub-step of O-contacting preferably results in a composition comprising acesulfame K or a derivative thereof, sulphuric acid and H₂A mixture of O. In and H₂H is preferably selected for use in the substep of O-contact₂The amount of O is such that the resulting mixture contains sulfuric acid H₂The weight ratio of O is 1:10 to 10:1, preferably 1:3 to 5:1, more preferably 1:1 to 3: 1. In one embodiment, with H₂The substep of O-contacting is performed as a continuous process. In this embodiment, H is adjusted₂The flow rate of O is used to set the sulfuric acid and H₂The proportion of O.

In one embodiment, H is used for the hydrolysis substep₂O is a gas phase. In one embodiment, H is used for the hydrolysis substep₂O is a liquid phase. In one embodiment, H is used for the hydrolysis substep₂O includes gas and liquid phases.

Reactor with a reactor shell

The contacting step a is preferably carried out in a reactor. The reactor is preferably constructed and adapted to withstand elevated pressures and temperatures. In one embodiment, the reactor is configured and adapted to withstand the temperature employed in the contacting step a. In another embodiment, the reactor is constructed and adapted to withstand temperatures up to 140 ℃, preferably 175 ℃, more preferably up to 200 ℃. In one embodiment, the reactor is constructed and adapted to withstand the pressure employed in the contacting step a. In another embodiment, the reactor is configured and adapted to withstand pressures of up to 1.6MPa, preferably up to 2.5MPa, more preferably up to 3.2 MPa.

In one embodiment, the reactor is a tubular reactor, preferably a cylindrical tubular reactor. In one embodiment, the reactor comprises a tube, preferably a cylindrical tube. The interior of a tube or tubular reactor is also referred to as a bore. The tube is preferably adapted and configured to cause a pressure drop between the reactor and the outside of the reactor, preferably a pressure drop of more than 0.05 MPa. The preferred tube is adapted and configured to cause spraying of the product.

The reactor preferably comprises a mixer, preferably a static mixer.

Contacting the first and second streams

The first stream and the second stream are contacted in a loop. The first stream comprises sulfuric acid and the second stream comprises ammonia. The contacting preferably produces diammonium sulfate. The first and second streams are not directly contacted, but are each introduced into a recycle stream where they react.

The reaction between sulfuric acid and ammonia is exothermic. The heat of reaction is preferably used to provide sufficient reaction temperature for the feedstock and to volatilize the fourth stream. Part or all of the third stream may be used as a heating medium to strip the spent sulfuric acid before it enters the reaction as the first stream. The heat of reaction thus reduces the energy consumption of the stripping step.

The recycle stream may be heated or cooled, particularly to accommodate the rate of volatilization from the third stream.

Step f-separation of the third stream

In the separation step f, the third stream is separated into a fourth stream and a fifth stream. Said fourth stream preferably comprises H₂O and amine, preferably as an azeotrope. The fourth stream is preferably the volatile phase. The preferred volatile phase is a gas. Preferably, the volatile phase is an azeotrope. The fourth stream can then be split to recover the amine. Said fifth stream preferably comprises H₂O and diammonium sulfate. The fifth stream is preferably a liquid. May then be substituted with H₂O, preferably steaming said fifth stream. The fifth stream may then be freed of H₂O, preferably solidified diammonium sulfate.

The separation of the third stream into a fourth stream and a fifth stream is preferably phase separated, preferably the fourth stream being the volatile phase and the fifth stream being the liquid. The preferred volatile phase is the gas phase. Preferably, the volatile phase is an azeotrope.

The separation step f is preferably carried out in a separator, preferably a phase separator. Another term for a separator is separator.

_{1 2}Step g-contacting the fifth stream with HO

May be in step g₁In the reaction of the fifth stream with H₂O, preferably to obtain an aqueous solution of diammonium sulfate. And H₂The O contacting preferably reduces the amine content of the fifth stream. In step g₁The amine removed from the fifth stream may be introduced into the fourth stream.

_{2 2}Step g-reduction of HO content

In step g₂The fifth stream may be treated to reduce its H₂The content of O. Step g₂Preferably a curing step. Reduction of H₂The content of O, preferably the curing, is preferably carried out by spray drying, preferably with a heated gas, preferably air. Preferred curing is one or more selected from the group consisting of: crystallization, precipitation and drying. Crystallization can be used to reduce diammonium sulfate or H in the fifth stream₂The content of substances other than O.

₂Step h-separation of amine and HO

The fourth stream may be separated into a sixth stream and a seventh stream, wherein the seventh stream comprises more H than the sixth stream₂O, and wherein the sixth stream comprises more amine than the seventh stream. The separation of step h is preferably a phase separation and distillation. The amine content of the sixth stream may be collected at the bottom of the distillation apparatus.

₃SO

By using SO₃The method as a starting material contributes to achieving at least one of the above objects. SO is preferably used in a molar amount at least equal to that of acetoacetamide-N-sulfonic acid or derivatives thereof₃Preferably in step a as SO₃The molar ratio to acetoacetamide-N-sulfonic acid or derivative thereof is from 1:1 to 20:1, preferably from 2:1 to 17:1, more preferably from 2.5:1 to 15:1, most preferably from 3:1 to 10: 1. In one embodiment, with acetoacetamide-N-sulfonic acidOr derivatives thereof, in about equimolar amounts₃. In this case, SO may be present₃Insufficient to form an adduct. In one aspect of this embodiment, H is not required₂And O contact. In one embodiment, a molar excess of SO is employed₃Preferably, in step a, SO₃The molar ratio to acetoacetamide-N-sulfonic acid or derivative thereof is from greater than 1:1 to 20:1, preferably from 2:1 to 17:1, more preferably from 2.5:1 to 15:1, most preferably from 3:1 to 10: 1.

In one embodiment of the present invention, SO is used in step a₃Provided in a first solvent.

In another embodiment, SO is used in step a₃Is provided as a liquid.

acetoacetamide-N-sulfonic acid or derivatives thereof

acetoacetamide-N-sulfonic acid or derivatives thereof are used in the process according to the invention. acetoacetamide-N-sulfonic acid is also of the formula CH₃COCH₂CONHSO₃H is known, the term acetoacetamide-N-sulfonic acid and the formula CH₃COCH₂CONHSO₃H may be used interchangeably herein.

Preferred derivatives of acetoacetamide-N-sulfonic acid are salts, preferably of formula CH₃COCH₂CONHSO₃ ^-M⁺. Preferred M⁺Is selected from Na⁺、K⁺、Ca⁺、Li⁺Ammonium and aliphatic ammonium. In this context, preferred aliphatic ammonium is one or more selected from the group consisting of: monoethylammonium, diethylammonium, triethylammonium, methylammonium, dimethylammonium and trimethylammonium. The preferred aliphatic ammonium is triethylammonium.

acetoacetamide-N-sulfonic acid or a derivative thereof may be obtained or formed in the process prior to step a of the process of the invention. A preferred route to form acetyl-acetamide-N-sulfonic acid or derivatives thereof is to react the amidosulfonic acid or derivative thereof with the acetoacetylating agent, preferably in about equimolar amounts. In this context, preferred derivatives of amidosulfonic acids are salts, preferably with a compound selected from the group consisting of Na⁺、K⁺、Ca⁺、Li⁺Ammonium and aliphatic ammonium. In this context, preferred aliphatic ammonium is one or more selected from the group consisting of: monoethylammonium, diethylammonium, triethylammonium, methylammonium, dimethylammonium and trimethylammonium. The preferred aliphatic ammonium is triethylammonium.

The preferred acetoacetylating agent is diketene.

In one embodiment, the acetoacetamide-N-sulfonic acid or derivative thereof used for contacting of step a is provided in a second solvent.

Solvent(s)

One or more solvents may be used in the process of the invention, for example to act as one or more of: as SO₃As a support for acetoacetamide-N-sulfonic acid or derivatives thereof, as a reaction medium in a reactor or a medium for providing evaporative cooling.

Preferred solvents for acetoacetamide-N-sulfonic acid or derivatives thereof are inert solvents. The inert solvent is preferably not chemically reactive with the acetoacetamide-N-sulfonic acid or derivative thereof. The inert solvent preferably does not chemically react with the acesulfame k or derivatives thereof. The inert solvent is preferably at most mixed with SO₃Minimal reaction, based on SO₃Preferably, no more than 1 wt% SO is consumed in one hour₃. Preferred solvents for acetoacetamide-N-sulfonic acid or derivatives thereof are one or more selected from the group consisting of: halogenated aliphatic hydrocarbons, aliphatic sulfoxides and aliphatic sulfones. Preferred halogenated aliphatic hydrocarbons have up to four carbon atoms, preferably one or more selected from the group consisting of: dichloromethane, chloroform and 1, 2-dichloroethane. The preferred aliphatic sulfoxide is dimethyl sulfoxide. The preferred aliphatic sulfone is sulfolane. In one embodiment, the solvent for acetoacetamide-N-sulfonic acid or derivative thereof is one or more selected from the group consisting of: dichloromethane and 1, 2-dichloroethane, preferably dichloromethane.

SO₃Preferred solvents of (3) are inert solvents. The inert solvent is preferably not chemically reactive with the acetoacetamide-N-sulfonic acid or derivative thereof. The inert solvent preferably does not chemically react with the acesulfame k or derivatives thereof. The inert solvent is preferablySelecting most and SO₃Minimal reaction, based on SO₃Preferably, no more than 1 wt% SO is consumed in one hour₃. For SO₃The preferred solvent of (b) may be an inorganic solvent or an organic solvent or both. The preferred inorganic solvent is SO₂. Preferred organic solvents are one or more selected from the group consisting of: halogenated aliphatic hydrocarbons, aliphatic sulfones. Preferred halogenated aliphatic hydrocarbons have up to four carbon atoms, preferably one or more selected from the group consisting of: dichloromethane, chloroform and 1, 2-dichloroethane. The preferred aliphatic sulfone is sulfolane. In one embodiment, the solvent is SO₂Or dichloromethane, or both.

In a preferred embodiment of the process of the invention, the same solvent is used for the acetoacetamide-N-sulfonic acid or derivative thereof and for the SO₃. In this context, the preferred solvent is a halogenated aliphatic hydrocarbon, most preferably dichloromethane.

In one embodiment, the contacting in step a is carried out in the presence of a reaction solvent. In one aspect of this embodiment, the reaction solvent is a compound. In another aspect of this embodiment, the reaction solvent is two or more compounds. In one aspect of this embodiment, the reaction solvent is an inert solvent. The inert solvent preferably does not chemically react with the acetoacetamide-N-sulfonic acid or derivative thereof. The inert solvent preferably does not chemically react with the acesulfame k or derivatives thereof. The inert solvent is preferably at most mixed with SO₃Minimal reaction, based on SO₃Preferably, no more than 1 wt% SO is consumed in one hour₃. In one aspect of this embodiment, the reaction solvent comprises a halogenated hydrocarbon. In one aspect of this embodiment, the reaction solvent is a halogenated hydrocarbon. In one aspect of this embodiment, the reaction solvent comprises dichloromethane. In one aspect of this embodiment, the reaction solvent is dichloromethane.

In one embodiment, step a is for contacting SO₃Provided in a first solvent. In one aspect of this embodiment, the first solvent is a compound. In another aspect of this embodiment, the first solvent is two or moreA plurality of compounds. In one aspect of this embodiment, the first solvent is an inert solvent. The inert solvent is preferably not chemically reactive with the acetoacetamide-N-sulfonic acid or derivative thereof. The inert solvent preferably does not chemically react with the acesulfame k or derivatives thereof. The inert solvent is preferably at most mixed with SO₃Minimal reaction, based on SO₃Preferably, no more than 1 wt% SO is consumed in one hour₃. In one aspect of this embodiment, the first solvent comprises a halogenated hydrocarbon. In one aspect of this embodiment, the first solvent is a halogenated hydrocarbon. In one aspect of this embodiment, the first solvent comprises dichloromethane. In one aspect of this embodiment, the first solvent is dichloromethane. In one aspect of this embodiment, the SO in the first solvent₃Is 0.05 to 20 moles, preferably 0.1 to 15 moles, more preferably 0.15 to 10 moles, most preferably 0.2 to 6 moles.

In one embodiment, the acetoacetamide-N-sulfonic acid or derivative thereof used for contacting of step a is provided in a second solvent. In one aspect of this embodiment, the second solvent is a compound. In another aspect of this embodiment, the second solvent is two or more compounds. In one aspect of this embodiment, the second solvent is an inert solvent. The inert solvent preferably does not chemically react with the acetoacetamide-N-sulfonic acid or derivative thereof. The inert solvent preferably does not chemically react with the acesulfame k or derivatives thereof. The inert solvent is preferably at most mixed with SO₃Minimal reaction, based on SO₃Preferably, no more than 1 wt% SO is consumed in one hour₃. In one aspect of this embodiment, the second solvent comprises a halogenated hydrocarbon. In one aspect of this embodiment, the second solvent is a halogenated hydrocarbon. In one aspect of this embodiment, the second solvent comprises dichloromethane. In one aspect of this embodiment, the second solvent is dichloromethane. In one aspect of this embodiment, the concentration of acetoacetamide-N-sulfonic acid or derivative thereof in the second solvent is from 0.02 to 5 moles, preferably from 0.03 to 3 moles, more preferably from 0.04 to 2 moles, and most preferably from 0.05 to 1.5 moles.

In one embodiment, the rootThe method of any one of the preceding embodiments, wherein step a is for the contacted SO₃Providing the acetoacetamide-N-sulfonic acid or derivative thereof in a first solvent for contacting with step a in a second solvent, and the first solvent and the second solvent are the same. In one aspect of this embodiment, the first solvent is a compound. In another aspect of this embodiment, the first solvent is two or more compounds. In one aspect of this embodiment, the first solvent is an inert solvent. The inert solvent preferably does not chemically react with the acetoacetamide-N-sulfonic acid or derivative thereof. The inert solvent preferably does not chemically react with the acesulfame k or derivatives thereof. The inert solvent is preferably at most mixed with SO₃Minimal reaction, based on SO₃Preferably, no more than 1 wt% SO is consumed in one hour₃. In one aspect of this embodiment, the first solvent comprises a halogenated hydrocarbon. In one aspect of this embodiment, the first solvent is a halogenated hydrocarbon. In one aspect of this embodiment, the first solvent comprises dichloromethane. In one aspect of this embodiment, the first solvent is dichloromethane.

Product of

The process of the present invention is preferably used for the preparation of 6-methyl-3, 4-dihydro-1, 2, 3-oxathiazin-4-one 2, 2-dioxide or a derivative thereof. 6-methyl-3, 4-dihydro-1, 2, 3-oxathiazin-4-one 2, 2-dioxide, also known as acesulfame k, is used herein as a synonym for 6-methyl-3, 4-dihydro-1, 2, 3-oxathiazin-4-one 2, 2-dioxide.

The product of the invention can be used as a food ingredient, preferably as a sweetener. Acesulfame k is often classified as a high intensity sweetener. In one embodiment, the acesulfame k or derivative thereof is non-toxic. In one embodiment, the acesulfame k or derivative thereof may be hydrolyzed, preferably at elevated temperatures, in an acidic medium, preferably resulting in a non-toxic hydrolysate.

Acesulfame k is usually prepared or usefully employed in the form of a salt. In one embodiment, the product is a salt of acesulfame k. Preferred salts of acesulfame k include acesulfame k and the conjugate base of a cation. In this context, preferred cations are those selected from the group consisting ofOne or more of the group: na (Na)⁺、K⁺、Ca⁺And aspartame, preferably K⁺. In one embodiment, the preferred cation is selected from the group consisting of Na⁺、K⁺And Ca⁺Group of (B), preferably K⁺. In another embodiment, the cation is aspartame. The salt is preferably formed by removing the acidic hydrogen from the nitrogen atom of acesulfame k or derivatives thereof. The product of the invention can be used as a food ingredient. In one embodiment, the acesulfame salt is non-toxic. In one embodiment, the acesulfame salt may be hydrolyzed in an acidic medium, preferably at elevated temperatures, preferably to produce a non-toxic hydrolysate.

Ethanesulfonamides can be prepared as adducts, either as end products or as intermediates. In one embodiment, the product is an adduct comprising acesulfame k or a derivative thereof. Preferred adducts form with electron acceptors, also known as lewis acids. In one aspect of this embodiment, the preferred adduct with SO₃And (4) forming. In one aspect of this embodiment, the product is 6-methyl-3, 4-dihydro-1, 2, 3-oxathiazin-4-one 2, 2-dioxide with SO₃SO, also known as acesulfame potassium₃An adduct. Acesulfame K SO₃The adduct may contain 1 or more SO₃An entity. In one aspect, acesulfame-K is SO₃The adduct may contain 1,2,3, 4, 5, 6, 7 or 8 SO₃An entity. In one aspect, acesulfame-K is SO₃The adduct may contain 1 to 8 SO₃Entities, preferably 1 to 7, more preferably 1 to 6, still more preferably 1 to 5. The product of the invention can be used as a food ingredient. In one embodiment, the adduct is non-toxic. In one embodiment, the adduct may be hydrolyzed to obtain a non-toxic hydrolysis product.

The product may be a mixture, preferably having one or more components selected from the group consisting of: acesulfame k, acesulfame k adducts and any other derivatives of acesulfame k. In one embodiment, the product comprises compounds with different degrees of addition. In one aspect of this embodiment, the product comprises acesulfame potassium and one or more acesulfame potassiumSami adducts, preferably with SO₃Exist together.

Test method

The following test methods were used for the features disclosed in this document. Without a test method, the ISO test method is applicable to the feature under test that was newly released prior to the earliest filing date of the present application. Without measurement, the temperature was 298.15K (25 ℃, 77 ℃ F.) and the absolute pressure was 100kPa (14.504psi, 0.986 atm).

Detection of chemical species and concentrations

-determining the content of Acesulfame K by a combination of HPLC and UV spectroscopy according to the procedure described in "Monace D Acesulfame-K USP-NF" published in the us pharmacopoeia and national prescription ". The most recently published monograph version of this document was used either at the earliest filing date or prior to the priority date of this document.

The content of acetoacetamide-N-sulfonate is calculated from the content of the process input stream.

-SO₃The content of (b) is determined by distillation.

Determination of the solvent content by gas chromatography and karl fischer titration.

The yield of acesulfame k was calculated based on the input content of sulfamic acid.

Reactor temperature

Based on the reactor pressure, the temperature in the reactor was calculated according to the An-toine equation as follows:

log₁₀p＝A–B/(C+T)

wherein p is in bar (10)⁵Pa), T is the reactor temperature in K, and the three constants have the following values:

A＝3.97323，B＝1016.865，C＝-56.623

reactor pressure and external pressure

Rosemount using piezoresistive pressure transmitter^TM3051 Coplanar^TMThe pressure is measured.

pH value

Using Rosemount^TMThe type 385 pH/ORP sensor measures pH.

Flow rate

Using Rosemount^TMModel 8732 electromagnetic flowmeter system measures flow.

Brief description of the drawings

The invention will now be further elucidated with reference to the drawing. The drawings and the accompanying description are exemplary and should not be taken as limiting the scope of the invention. The drawings and description focus on the features of the process related to the present invention and are not intended to be a comprehensive description of the process that has been developed. The skilled person is aware of the technical details required to carry out part of the process outside the scope of the invention, such as standard methods of distillation, phase separation and drying.

Fig. 1 is a schematic diagram illustrating the flow of material in a method according to the invention.

FIG. 2 is a schematic process flow diagram showing the steps of the present invention.

FIG. 3 is a graph showing the effect of water content on energy efficiency in diammonium sulfate production.

Figure 4 is a graph showing the effect of recycle ratio on sulfuric acid and ammonium sulfate conversion and pump parameters.