The method of obtaining polyoxyethyleneglycol esters

 

(57) Abstract:

The invention relates to an improved method for producing polyoxyethyleneglycol, in particular oxyalkylene, higher fatty alcohols, ALKYLPHENOLS, glycols, amines and carboxylic acids, highly effective nonionic surfactants. These compounds find wide application in various industries and household. Polyoxyethyleneglycol esters produced by interaction of oxides alkylene with compounds having a mobile hydrogen atom, at elevated temperature and pressure in the presence of an alkali metal alcoholate, in a reactor comprising one or more reactors displacement. As reactors using machines, in which the reaction volume is enclosed between the two surfaces of the heat exchanger. The method allows to increase the specific productivity of the reactor site, and allows the use of different raw materials. 8 C.p. f-crystals, 5 Il.

The invention relates to an improved method for producing polyoxyethyleneglycol esters (GE), which find wide application in various sectors of the economy, in particular, as detergents, textile sposaitalia oxide alkylene connections, having a mobile hydrogen atom (alcohols, glycols, phenols, carboxylic acids, amines, amides, and others) in a bubbling reactor properities action, equipped with a jacket and coils for heat dissipation of a chemical reaction, at a temperature of 80-230oC and a pressure of 0.2-0.5 MPa. (U.S. Pat. USA 2678935; Pat England 721778; Malkemus J. D, J. Am.Oil Chem. Soc. 33, 571, 1956; N. The Schoenfeld "Surfactants based on ethylene oxide), Chemistry, 1982, S. 66). Specific performance data of the reactor does not exceed 0,025 kg oxide with one m3reaction volume in one second (0.025 kg/m3C). These methods are the basis of most existing in Russia and abroad production of GE (fatty alcohol ethoxylates, neonols, stearoks, glycols, and others).

The main disadvantages of these methods is the low specific productivity, increased fire and explosion hazards due to contact of the gaseous oxide alkylene with moving parts mixing device as well as the loss of ethylene oxide at the unloading stage of the reaction products.

Known methods for producing GE, in which for increasing the specific productivity of the reactor site, the reaction mixture is circulated through an external heat exchanger (U.S. Pat. Germany 855111; Fri quantities of 0.1 kg/m3C.

Known liquid-phase continuous interactions of the compounds with a movable hydrogen atom from the oxide alkylene in tubular reactors small diameter of 0.004-0,009 m (Pat Germany 735418, application Germany 2358874; U.S. Pat. USA 3436425, 3436426; N. The Schoenfeld "Surfactants based on ethylene oxide), Chemistry, 1982, S. 68-69). Specific performance of these reactors is 2-17 kg/m3C.

The main disadvantage of these methods is the high sensitivity of the reactor site to fluctuations in process parameters: the initial temperature of the mixture, coolant temperature, concentration of catalyst, etc., (the so-called "parametric sensitivity" - D. Perlmutter. Stability of chemical reactors. L., Chemistry, 1976). From the description of these methods can be seen that increasing the temperature by 10oWith the temperature of the reaction mass increases by more than 200oAnd industrial implementation of this method, this fact will lead to lower quality products.

Another disadvantage of this method is the need to use as reactor tubes of small diameter, which is high hydrauliczne was implemented on an industrial scale.

The closest analogue is the way to obtain polyoxyethyleneglycol esters by the interaction of oxides alkylene with compounds having a mobile hydrogen atom in the liquid phase at elevated temperature and pressure in reactor, which can be viewed as a cascade of series-connected tubular reactors wipe with a tube diameter of a 0.012-0.02 m and fractional (dispersed) submission oxide alkylene. While the number of entry points oxide can reach 30 (U.S. Pat. USA 2988572). To reduce the parametric sensitivity it is recommended to carry out the process at a concentration of oxide at the entrance to each reactor 1-7 wt.%. and turbulent motion of the reaction mixture in the tube (Re>10000). Specific performance of this reactor site reaches 0.68 kg/m3C. the Disadvantage of this method is relatively low specific capacity, and the presence of a large number of entry points oxide, which in turn complicates the process.

The task of this method is the increase in the specific productivity of the process, which is achieved by the interaction of oxides alkylene with compounds having a mobile hydrogen atom in the liquid phase at elevated so the e reactor using machines, in which the reaction volume is enclosed between the two heat transfer surfaces.

The process can be carried out in one reactor. However, it is preferable to conduct the process in a cascade of reactors displacement with fractional (dispersed) submission oxide alkylene.

As reactors, it is desirable to use one or more heat exchangers connected in a series-parallel circuit.

As heat exchangers you can use the standard plate and spiral heat exchangers (the Basic processes and apparatus of chemical technology. Manual on design. Ed. by D. T. N., Professor Y. I. of Ditmarsch Moscow, Chemistry, 1983, S. 29-31), as well as tubular heat exchangers. At the same time as tubular heat exchangers, it is preferable to use one or more heat exchangers type "pipe in pipe", is additionally placed in the casing.

In Fig.1(a,b) shows one heat exchanger pipe in pipe", placed in the casing with a diameter of D3. In Fig.1 depicts several heat exchangers "pipe in pipe", placed in one casing with a diameter of D4.

The heat of the chemical reaction may be carried out at the expense forced disengage. Thus the heat exchange surface may be washed one coolant (Fig.1) or different fluids (Fig.1 a,C) having the same or different temperatures.

The following examples illustrate the method:

Example 1

The process of obtaining polyoxyethyleneglycol esters is carried out in a reactor site, consisting of four identical tubular reactors (Fig.1), the following parameters: D1=25x2 mm, D2=38x3.5 mm, D3=57x4 mm, L=12 m wiring Diagram of the reactor is shown in Fig.2. The total reaction volume is:

< / BR>
where n is the number of reactors in the reactor site.

As compounds with a movable hydrogen atom use alcohols fraction C12-C14with an average molecular mass MM=200.

The original alcohols with diluted catalyst NaOH (0.2%wt.) speed (Gc) 0,0601 kg/s and ethylene oxide with a speed of (Go) 0,0397 kg/s fed into the mixer where the mixture is fed to the inlet of the first reactor. The temperature of the mixture at the entrance to the reactor site 125oC. Leaving the first reactor, the mixture is successively directed to the input of the second reactor and then to the input of parallel third and fourth reactors.em coolant temperature 165oWith in the tube space and the casing. As calanolides use water under pressure. At the outlet of the reactor node speed (GCR) 0,0998 kg/s selected GE - colorless addition products of 3 moles of oxide to one pray alcohols (degree oksietilirovannye, 3) with a hydroxyl number (MS) equal to 169 and an average molecular mass (MM), equal to 332. The degree of conversion of ethylene oxide (X) of 99.1%. Specific productivity (Gy) reactor site attached to ethylene oxide is:

Gy=G0X/V=0,3940,991/0,01266=3,11 kg/(m3C)

When the temperature of the coolant at the 5oWith the temperature in the reactor does not exceed 240oWith the degree of conversion X=99,99. At the reactor exit select high-quality colorless product with GC=170, which indicates a low parametric sensitivity of the reactor site to fluctuations in the temperature of the coolant.

Example 2

The process of obtaining polyoxyethyleneglycol esters is carried out in the reactor unit, which consists of five tubular reactors (Fig.1,a), the following parameters: D1= 25x2 mm, D2=38x3.5 mm, D3=57x4 mm, L=12 m, the Total volume of the reactor site is 0,01583 m3. the use alcohols fraction C12-C14with an average molecular mass MM=200.

The original alcohols with diluted catalyst NaOH (0,22%wt.) speed (Gc) 0,0257 kg/s and ethylene oxide with a speed of (GO,1) 0,01246 kg/s fed into the mixer where the mixture is directed to the input of the first reactor of the cascade. The temperature of the mixture at the entrance to the reactor site 120oC. Leaving the first reactor, the mixture is successively directed to the input of the second reactor. Leaving the second reactor, the reaction mass is mixed in the mixer with a stream of ethylene oxide (Gof 0.2), equal 0,0215 kg/s and is directed to the input of the third reactor, and then to the input of parallel fourth and fifth reactors. The pressure in reactor - 40 at. The temperature in the reactor is supported in the interval 120-225oWith through coolant - water pressure in the pipe space (stream III, Fig.1A) with a temperature of 160oAnd the casing of the reactor (stream II, Fig.1A) with a temperature of 175oC. At the outlet of the reactor node speed (GCR) 0,05966 kg/s selected GE - addition products of ethylene oxide to alcohols (6, MS=122; MM=459). The degree of conversion of ethylene oxide (X) 99,0%. The specific productivity of the reactor site attached to ethylene oxide equal the e exceed 245oWith the degree of conversion X=99,99. At the exit of the reactor taken colorless product with GC=121.

Example 3

The process of obtaining polyoxyethyleneglycol esters is carried out in reactor consisting of three tubular reactors (Fig.1,a) and two tubular reactors (Fig. 1. in), the following parameters: D1=20x2 mm, D2=38x3.5 mm, d3=76x4 mm, L=12 m wiring Diagram of the reactor is shown in Fig.4. The reaction volume is equal 0,0264 m3.

As compounds with a movable hydrogen atom use isononylphenol with a molecular mass MM=220.

Source isononylphenol with diluted catalyst - CON (0,3%wt.) speed (Gwith) 0,0214 kg/s and ethylene oxide with a speed of (Ga 0.1) 0,0081 kg/s is sent to the mixer where the mixture is fed to the inlet of the first reactor of the cascade. The temperature of the mixture at the entrance to the reactor site 118oC. Leaving the first reactor, the reaction mass is mixed in the mixer with the flow of the oxide (Gof 0.2) 0,0128 kg/s and is directed to the input of parallel second reactor and the third reactor. Coming out of the second and third reactors of the reaction mass is mixed in the mixer with a stream of ethylene oxide (Gof 0.2), equal 0,0225 KGT. The temperature in the reactor is supported in the interval 120-235oWith a due supply of water under pressure into the tube space of the reactor with a temperature of 150-160oC. At the outlet of the reactor site selected GE - colorless addition products of ethylene oxide to isononylphenol (10; GC=85; MM=659) at a rate of GCR=0,064 kg/s conversion rate of ethylene oxide (X) of 98.5%. The specific productivity of the reactor site attached to ethylene oxide is equal to Gy=l,53 kg/(m3C).

When the temperature of the coolant at the 5oWith the temperature in the reactor does not exceed 255oWith the degree of conversion is equal to X=99,99. At the exit of the reactor taken colorless product with GC=83.

Example 4

The process of obtaining polyoxyethyleneglycol esters is carried out in reactor consisting of:

three series-connected tubular reactors (Fig.1,in) parameters: D1=25x2 mm, D2=38x3.5 mm, D3=57x4 mm, L=12 m;

four parallel-connected tubular reactors (Fig.1,a) parameters: D1=25x2 mm, D2=38x3.5 mm, D3=57x4 mm, L=12 m;

one reactor (Fig.1,with the following parameters: D1=25x2 mm, Dthe ditch is shown in Fig.5. The reaction volume is equal 0,0443 m3.

Source isononylphenol with diluted catalyst NaOH (0.45%of wt. ) speed (Gc) 0,0092 kg/s and ethylene oxide with a speed of (Ga 0.1) 0,0051 kg/s is sent to the mixer where the mixture is fed to the inlet of the first reactor of the cascade. The flow of the reaction mixture leaving the second reactor is mixed in the mixer with the flow of the oxide (Gof 0.2) 0,0061 kg/s and is directed to the input of the third reactor. The flow of the reaction mixture leaving the third reactor, mixed in the mixer with the flow of the oxide (Gfor 0.3) 0,0109 kg/s and is directed to the input of parallel fourth, fifth, sixth and seventh reactors. Emerging from these reactors, the reaction mixture is mixed in the mixer with the flow of the oxide (Gfor 0.4) 0.015 kg/s and is directed to the input of the last reactor (Fig.1.C). The pressure in reactor - 40 at. The temperature in the reactor support in the range of 120-240oWith a due supply of water under pressure into the tube space and the casing temperature 115-165oC. At the outlet of the reactor site selected GE - colorless addition products of ethylene oxide to isononylphenol (6; GC=52; MM=1080) with a speed of GCR= 0,0463 kg/s conversion rate of ethylene oxide (X)UP>3C).

Example 5

The process is carried out analogously to example 2. In connection with a movable hydrogen atom use higher amines WITH12-C14with an average molecular mass MM=198. The concentration of the catalyst of 0.07 wt.%. The feed speed of the original amine - 0,027 kg/sec total flow rate of the ethylene oxide - 0,048 kg/s (0,016 and to 0.032 kg/s). The pressure in reactor - 30 at. Coolant temperature 145-158oC. the Temperature in the reactor 120-235oC. At the outlet of the reactor site selected GE - addition products of ethylene oxide to higher amines (8; MM=550) with a speed of GCR=0,075 kg/s conversion rate of ethylene oxide (X) 98,9%. The specific productivity of the Gy=3.0 kg/(m3C).

Example 6

The process is carried out in a reactor consisting of two identical series-connected heat exchangers with a total volume of 0.017 m3. In connection with a movable hydrogen atom using stearic acid, MM= 284,5. The feed rate of stearic acid - 0,058 kg/sec total flow rate of the ethylene oxide - 0,054 kg/s (and 0,019 0,035 kg/s). The pressure in reactor - 40 at. The temperature in the reactor is supported in the interval 120-235oWith due to the supply of heat is tion of ethylene oxide to stearic acid (6; MM=549). The degree of conversion of ethylene oxide (X) 99,4%. The specific productivity of the Gy=3.15 kg/(m3c).

Example 7

The process is carried out in a reactor consisting of a single spiral heat exchanger with 0,01 m3. As starting substances used alcohols fraction10-C18with an average molecular mass MM=214 and propylene oxide. The concentration of KOH in the original spirits - 0.1%wt. The feed rate of alcohol - 0,0418 kg/s feed Rate of propylene oxide - 0,034 kg/s Pressure in reactor - 20 at. The temperature in the reactor is supported in the interval 120-225oWith through coolant - duterme with temperature 135-160oC. At the outlet of the reactor site selected GE - addition products of propylene oxide to alcohols (3; GC=150; MM=374). The degree of conversion of propylene oxide (X) of 99.3%. The specific productivity of the Gy=3,38 kg/(m3C).

The process in this way allows you to increase the specific productivity of the reactor site from 0.63 to 0.83-3,38 kg/(m3(C) at low parametric sensitivity of the reactor site to fluctuations in the temperature of the coolant.

In addition, by changing the circuit connections of the reactor cascade, and distributing the flows oxide what I polyoxyethyleneglycol esters from different feedstock (alcohols, the alkyl phenols, carboxylic acids, amines).

1. The method of obtaining polyoxyethyleneglycol esters by the interaction of oxides alkylene with compounds having a mobile hydrogen atom in the liquid phase at elevated temperature and pressure in the presence of alkali metal alcoholate in reactor comprising one or more reactors displacement, and the heat of chemical reaction via heat exchange surface, characterized in that as reactors displacement using machines, in which the reaction volume is enclosed between the two heat transfer surfaces.

2. The method according to p. 1, characterized in that the interaction is carried out in a cascade of reactors connected in a series-parallel circuit.

3. The method according to p. 1, characterized in that the interaction is carried out in a cascade of reactors displacement with fractional (dispersed) submission oxide alkylene.

4. The method according to p. 1, characterized in that as reactors displacement using heat exchangers.

5. The method according to p. 4, characterized in that as heat exchangers use a plate, spiral or tubular heat exchangers.

6. The method according to p. 5, distinguish the in-pipe", placed in the casing.

7. The method according to p. 6, characterized in that the heat of chemical reactions carried out due to the forced movement of the fluid in the casing and/or the tube of the heat exchanger.

8. The method according to p. 6, characterized in that the heat of chemical reactions carried out due to the forced movement of the fluid in the pipe of the heat exchanger and/or boiling of the coolant in the jacket.

9. The method according to p. 7, characterized in that the heat exchange surface is washed one or different fluids with the same at different temperatures.

 

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