Joint production method and device for aziridine, piperazine and triethylenediamine

Abstract

Disclosed are a joint production method and device for aziridine, piperazine and triethylenediamine. The method comprises: reaction 1, preparing piperazine and triethylenediamine by taking ethanol amine as a raw material under the existence of a cyclamine catalyst; reaction 2, preparing aziridine by taking the ethanol amine as the raw material under the existence of a catalyst B; and taking heat released in the reaction 1 as a heat source of heat absorption in the reaction 2. The device comprises a reactor 1 for carrying out the reaction 1 and the heat exchange between reaction materials of the reaction 1 and the raw material of the reaction 2 and a reactor 2 for carrying out the reaction 2. According to the present invention, the same raw material, namely the ethanol amine is adopted, aziridine, piperazine and triethylenediamine can be produced in a joint manner, the heat released in the reaction 1 is used for preheating materials in the reaction 2, so that heat coupling between the reactions is implemented, energy conservation is facilitated and competitiveness of the device is improved.

Claims

1. A joint production method for preparation of aziridine, piperazine and triethylenediamine, the method comprising: a first reaction comprising preparing piperazine and triethylenediamine by taking ethanol amine as a raw material in the presence of a cyclamine catalyst; and a second reaction comprising preparing aziridine by taking ethanol amine as a raw material in the presence of a catalyst B; wherein the catalyst B is Ti.sub.aP.sub.bB.sub.cX.sub.dY.sub.eO.sub.f, wherein: X is an alkaline earth metal, Y is an alkaline metal, O is an oxygen element; a, b, c, d, e, and f are the mole ratios of each element atom, and a=1, b=0.020.2, c=0.0020.02, d=0.010.1, e=0.0010.01, and f is dependent on a, b, c, d, and e; and the heat released in the first reaction is used as a heat source for the second reaction.

2. The joint production method for preparation of aziridine, piperazine and triethylenediamine of claim 1, wherein the temperature of the first reaction ranges from 300 C. to 400 C.

3. The joint production method for preparation of aziridine, piperazine and triethylenediamine of claim 1, wherein the temperature of the second reaction ranges from 350 C. to 450 C.

4. The joint production method for preparation of aziridine, piperazine and triethylenediamine of claim 1, further comprising a preparation method for the catalyst B comprising: mixing a compound comprising X, a compound comprising Y, a metatitanic acid, a phosphate, and a boronic acid well and adding graphite, thereby obtaining a first mixture; compressing the first mixture and shaping, thereby obtaining a shaped mixture; and calcining the shaped mixture in the presence of oxygen at a temperature ranging from 300 C. to 400 C. followed by further calcining at a temperature ranging from 600 C. to 900 C., thereby obtaining the catalyst B; wherein the compound comprising X is an oxide, a hydroxide, a halide, a nitrate, a carbonate, or a sulfate of X; the compound comprising Y is an oxide, a hydroxide, a halide, a nitrate, a carbonate, or a sulfate of Y; the phosphate is ammonium phosphate, diammonium phosphate, or ammonium dihydrogen phosphate; and the graphite is 1%4% by mass of the first mixture.

5. The joint production method for preparation of aziridine, piperazine and triethylenediamine of claim 1, further comprising a process of separating products, the process comprising: mixing the reaction products obtained in the first reaction and the second reaction, thereby obtaining a first mixture stream; flashing the first mixture stream thereby separating nitrogen and obtaining a second mixture stream; distilling the second mixture stream, thereby removing ammonia and obtaining a third mixture stream; separating and obtaining aziridine from the third mixture stream, thereby obtaining a fourth mixture stream; and separating and obtaining piperazine and triethylenediamine from the fourth mixture stream.

Description

DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a schematic flow chart of the production process of aziridine, piperazine and triethylenediamine.

SPECIFIC MODE FOR CARRYING OUT THE PRESENT INVENTION

(2) Reaction 1 is carried out at the reaction temperature of 300 C. to 400 C. by taking ethanol amine as a raw material in the presence of the cyclamine catalyst, so that piperazine and/or triethylenediamine may be produced with high selectivity. The reaction (1) is an exothermic reaction:

(3) ##STR00001##

(4) The ethanol amine as a raw material is reacted at the reaction temperature of 350 C. to 450 C. in the presence of the catalyst B, so that aziridine may be produced with high selectivity. The reaction (2) is an endothermic reaction:

(5) ##STR00002##

(6) The heat coupling between the above reactions may be achieved by using ethanol amine as a raw material. At the same time, aziridine, piperazine and triethylenediamine may be produced jointly from the same raw material, thereby improving the competitiveness of the device.

(7) According to the present invention, monoethanolamine is used as a raw material. Isopropanolamine, 2-methylamino-propanol, and other amino alcohol compounds may also be used.

(8) The cyclamine catalyst according to the present invention is the catalyst as described in CN102000602A.

(9) In the catalyst B according to the present invention, preferably, X is magnesium, Y is cesium, b=0.2, c=0.01, d=0.1, e=0.01, f=2.62, or X is barium, Y is potassium, b=0.05, c=0.02, d=0.1, e=0.01, f=2.27.

(10) The structured packing according to the present invention is stainless steel wire mesh or plate wave packing.

(11) The reaction process performed in the device according to the present invention is illustrated as follows:

(12) As described in FIG. 1, a preheated feed stream E mainly composed of ethanol amine, water, and nitrogen or ammonia as an inert gas are introduced into a reactor 1 with tube pass and shell pass structure, the tube pass of which is filled with a cyclamine catalyst; the contact reaction of the feed stream E, which is an exothermic reaction, is carried out in the presence of the cyclamine catalyst, and the heat released is conducted to and thereby preheats the materials of the shell pass through the tube wall of the tube pass of the reactor 1; the obtained products stream F comprising the inert gas, water, ammonia, unreacted ethanol amine and products, i.e., piperazine, triethylenediamine and a small amount of ethylenediamine, hydroxyethyl piperazine, and aminoethyl piperazine is discharged from the bottom of the reactor 1 and introduced into the combination separation unit.

(13) A preheated feed stream A mainly composed of ethanol amine, and nitrogen as an inert gas are introduced into the shell pass of the reactor 1, and preheated by the heat conducted through the tube pass of the reactor 1; the preheated mixture is discharged from the shell pass, introduced into an intermediate heat exchanger 6 through a pipeline B, and further heated to a certain temperature, then introduced into a reactor 2 with tube pass and shell pass structure through a pipeline C, wherein the tube pass of the reactor 2 is filled with a catalyst B; the contact reaction of a feed stream C is carried out in the presence of the catalyst B, and the obtained products stream D comprising the inert gas nitrogen, water, unreacted ethanol amine, and products i.e., aziridine, and the light component ethylene amine is discharged from the bottom of the reactor 2 and introduced into the combination separation unit.

(14) The reaction products stream introduced into the combination separation unit comprises the inert gas nitrogen, ammonia, water, aziridine, unreacted ethanol amine, products i.e., piperazine, triethylenediamine, ethylenediamine, aminoethyl piperazine, and hydroxyethyl piperazine. The reaction products stream is separated in a combination separation unit which comprises a flash unit 3, an aziridine separation unit 4, and a polyamine separation unit 5. The aziridine product stream is collected in a liquid phase from a side-draw of the aziridine separation unit 4, and piperazine and triethylenediamine are collected in a gas phase from a side-draw of the polyamine separation unit 5.

(15) The present invention will be further explained and described below with reference to the following preferable examples provided by the inventor, but is not limited thereto.

Example 1

(16) Referring to FIG. 1, the process of the reaction (1): a feed stream E with a flow rate 2876.34 kg/h was preheated to 330 C., introduced to the tube pass of the reactor 1 in which a cyclamine catalyst was filled; the contact reaction of the feed stream E was carried out in the presence of the cyclamine catalyst under a reaction pressure of 1.0 MPa with a heat release power of 118 kW; and the obtained products stream F was discharged from the bottom of the reactor 1 and introduced into a separation unit.

(17) The composition of the feed stream E by mass percentage was:

(18) NH.sub.3: 15.1%, MEA: 71.3%, and H.sub.2O: 13.5%.

(19) The composition of the products stream F by mass percentage was:

(20) NH.sub.3: 15.0%, MEA: 24.0%, EDA: 5.0%, H.sub.2O: 27.0%, PIP: 14.7%, AEP: 2.6%, TEDA: 10.3%, HEP: 0.9%, and noncondensable gas: 0.3%.

(21) The process of the reaction (2): a feed stream A with a flow rate 13853.48 kg/h was preheated to 290 C., introduced to the shell pass of the reactor 1, heated to a temperature of 314 C. through the heat conducted by the tube pass of the reactor 1, discharged from the shell pass, then introduced into an intermediate heat changer 6 through a pipeline B and further heated to a temperature of 380 C. with an heating power of 329 kW, and introduced into a reactor 2 filled with a catalyst B through a pipeline C, to carry out the contact reaction under a reaction pressure of 0.1 MPa; the obtained products stream D was discharged from the bottom of the reactor 2 and introduced into a separation unit.

(22) The composition of the feed stream C by mass percentage was:

(23) N.sub.2: 17.9% and MEA: 82.1%.

(24) The composition of the products stream D by mass percentage was:

(25) N.sub.2: 82.1%, H.sub.2O: 2.37%, aziridine: 4.67%, MEA: 9.84%, ethylene amine: 0.35%, piperazine and derives thereof: 0.41%, and others: 0.3%.

(26) The heat released from the process of the reaction (1) was used as the heat required for the process of the reaction (2), so that approximately 26.4% of energy was saved.

(27) In this Example 1, the flash unit 3 was a flash tower, wherein the flash tower had a theoretical plate number of 2, a temperature of 20 C., and a pressure of 2.0 MPa.

(28) The composition of the feed stream G by mass percentage was:

(29) N.sub.2: 99.5% and others: 0.5%.

(30) The composition of the feed stream H by mass percentage was:

(31) N.sub.2: 4.1%, H.sub.2O: 9.3%, aziridine: 21.0%, ethanol amine: 38.7%, piperazine: 12.0%, triethylenediamine: 8.3%, ethylenediamine: 4.1%, aminoethyl piperazine and hydroxyethyl piperazine: 2.2%, and ethylene amine: 0.35%.

(32) The aziridine separation unit 4 was a rectifying tower filled with structured packing, wherein the rectifying tower had a theoretical plate number of 45, a top temperature of 23.3 C., a bottom temperature of 226 C., and a pressure of 2.0 MPa. The feeding location was at the 18.sup.th theoretical plate. Ammonia in a gas phase and remaining nitrogen were collected from the top of the rectifying tower, and an aziridine product stream was collected in a liquid phase from a side-draw, the collection position from the side-draw was located at the 3.sup.th theoretical plate.

(33) The composition of the feed stream M by mass percentage was:

(34) N.sub.2: 93.2%, NH.sub.3: 5.4%, and aziridine: 1.3%.

(35) The composition of the feed stream N by mass percentage was:

(36) Aziridine: 99.8%, and others: 0.2%.

(37) The composition of the feed stream Z by mass percentage was:

(38) H.sub.2O: 12.5%, ethanol amine: 51.8%, piperazine: 16.0%, triethylenediamine: 11.1%, ethylenediamine: 5.49%, and aminoethyl piperazine and hydroxyethyl piperazine: 3.0%.

(39) The polyamine separation unit 5 was a rectifying tower filled with structured packing, wherein the rectifying tower had a theoretical plate number of 60, a top temperature of 86.3 C., a bottom temperature of 149.4 C., and a pressure of 50 kPa. The feeding location was at the 40.sup.th theoretical plate. A feed stream 12 comprising ethanediamine and water was collected from the top of the rectifying tower; a piperazine product stream was collected in a gas phase from a side-draw at the 30.sup.th theoretical plate; a mixture of triethylenediamine and ethanol amine was collected from a side-draw at the 48.sup.th theoretical plate; and the remaining ethanol amine, aminoethyl piperazine, and hydroxyethyl piperazine were collected from the bottom of the rectifying tower.

(40) The composition of the feed stream P by mass percentage was:

(41) Ethanediamine: 30.3% and H.sub.2O: 69.5%.

(42) The composition of the feed stream Q by mass percentage was:

(43) Piperazine: 99.1% and others: 0.9%.

(44) The composition of the feed stream R by mass percentage was:

(45) Triethylenediamine: 56.7%, ethanol amine: 43.2%, and others: 0.1%.

(46) The composition of the feed stream S by mass percentage was:

(47) Ethanol amine: 93.4%, aminoethyl piperazine and hydroxyethyl piperazine: 5.3%, and others: 1.3%.

Example 2

(48) Referring to FIG. 1, the process of the reaction (1): a feed stream E with a flow rate 4,183.02 kg/h was preheated to 330 C., introduced to the tube pass of the reactor 1 in which a cyclamine catalyst was filled; the contact reaction of the feed stream E was carried out in the presence of the cyclamine catalyst under a reaction pressure of 1.0 MPa with a heat release power of 173.3 kW; and the obtained products stream F was discharged from the bottom of the reactor 1 and introduced into the combination separation unit.

(49) The composition of the feed stream E by mass percentage was:

(50) NH.sub.3: 14.3%, MEA: 72.0% and H.sub.2O: 13.7%.

(51) The composition of the products stream F by mass percentage was:

(52) NH.sub.3: 14.5%, MEA: 24.2%, EDA: 4.3%, H.sub.2O: 26.4%, PIP: 15.4%, AEP: 1.6%, TEDA: 13.3%, HEP: 0%, and noncondensable gas: 0.3%.

(53) The process of the reaction (2): a feed stream A with a flow rate 20,333.3 kg/h was preheated to 290 C., introduced to the shell pass of the reactor 1, heated to a temperature of 314 C. through the heat conducted by the tube pass of the reactor 1, discharged from the shell pass, then introduced into an intermediate heat changer 6 through a pipeline B and further heated to a temperature of 400 C. with an heating power of 618.3 kW, and introduced into a reactor 2 filled with a catalyst B through a pipeline C to carry out a contact reaction under a reaction pressure of 0.1 MPa; and the obtained products stream D was discharged from the bottom of the reactor 2 and introduced into the combination separation unit.

(54) The composition of the feed stream C by mass percentage was:

(55) N.sub.2: 17.9% and MEA: 82.1%.

(56) The composition of the products stream D by mass percentage was:

(57) N.sub.2: 81.6%, H.sub.2O: 2.58%, aziridine: 4.62%, MEA: 8.32%, ethylene amine: 0.55%, piperazine and derives thereof: 0.82%, and others: 1.51%.

(58) The heat released from the process of the reaction (1) was used as the heat required for the process of the reaction (2), so that approximately 21.9% of energy was saved.

Example 3

(59) Referring to FIG. 1, the process of this Example 3 was substantially the same as that of Example 1 except that the feed stream E was preheated to a temperature of 360 C.; the feed stream A was preheated to a temperature of 300 C., introduced into the shell pass of the reactor 1, and heated to a temperature of 329 C. by the heat conducted through the tube pass of the reactor 1.

(60) The heat released from the process of the reaction 1 was 224.3 kW, and the heating power of the intermediate heat exchanger 6 was 348.3 kW.

(61) The heat released from the process of the reaction (1) was used as the heat required for the process of the reaction (2), so that approximately 39.1% of energy was saved.

Example 4

(62) Referring to FIG. 1, the process of this Example 4 was essentially the same as that of Example 1 except that the feed stream E was preheated to a temperature of 340 C.; the feed stream A was preheated to a temperature of 280 C., introduced into the shell pass of the reactor 1, heated to a temperature of 321 C. by the heat conducted through the tube pass of the reactor 1, discharged from the shell pass, introduced into the intermediate heat exchanger 6 with a heating power of 468.2 kW through a pipeline B and further heated to a temperature of 400 C.

(63) The heat released from the process of the reaction 1 was 198.9 kW.

(64) The heat released from the process of the reaction (1) was used as the heat required for the process of the reaction (2), so that approximately 29.8% of energy was saved.