Method of producing nitroparaffins

专利摘要:
1. METHOD OF OBTAINING NITROPARAPINS by nitrating propane or ethane-propane mixture with nitrogen dioxide in the gaseous phase under a pressure of 10-60 bar in the presence of a sour or inert gas of hydrogen-containing at 275-460 0, tl and h and s and In order to increase the content in the target product of nitromethane, the process is carried out in the presence of 2-nitropropane, recycled after separation of the reaction streams.
公开号:SU1199198A3
申请号:SU792747454
申请日:1979-04-04
公开日:1985-12-15
发明作者:Лоноре Пьер；Кибель Жак；Жакино Бернар
申请人:Сосьете Шимик Де Ля Гранд Паруасс,Азот Э Продюи Шимик (Фирма)；
IPC主号:

专利说明:

; about with
with
eo
, 2. A method according to claim 1, characterized in that the amount of recycled 2-nitropropane is 13-120% of the amount of nitroproduced products, wherein
recycling is carried out in relation to the total mass of nitroparaffins obtained, successively in succession with the preparation of nitroparaffins.
This invention relates to a process for the production of nitroparaffins by nitration in the gas phase under pressure.
The purpose of the invention is to increase the content of nitromethane in a mixture of nitroparaffins obtained by nitrating propane or ethane-propane mixture.
Examples illustrating the invention.
Example 1: Effect of reaction temperatures.
Propane is nitrated at a pressure of 300 bar at a pressure of 10 bar, and the contact times with the nitrucic agent (nitro-oxide) are 7c.
The results of the experiments are presented in table. 1 (the weight ratios at the inlet to the reactor between the nitrating agent and propane, air and propane, the composition of the liquid phase tf L, expressed in mass percent and the weight consumption of propane and nitrodioxide, are related to the kilogram of the total amount of nitroparaffins Nif produced).
. As can be seen from the data table. 1, an increase in temperature leads to an increase in the amount of nitromethane in the condensed waste stream and, accordingly, to an insignificant increase in nitroethane and 1-nitropropane and a rapid and significant decrease in the amount of 2-nitropropane.
FIG. Figure 1 shows the dependence of nitroparaffin formation on the reaction temperature: 2-nitropropane (2-NP) corresponds to curve 1; nitromethane (NM) - curve 2; 1-nitrolropane (1-NP) - curve 3; nitroethane (NE) - curve 4.
I;
In FIG. 2, the mass flow rate M (%) of propane and nitrodioxide is plotted on the ordinate axis, the temperature T (° C) is plotted on the abscissa axis. Curve 1 corresponds to propane; curve 2 corresponds to nitrodioxide.
Example 2. Recycling of 2-nitroparaffin. A series of experiments was carried out on propane nitration at a pressure of 10 bar, a contact time of 7 s and a nitrodioxide / / propane ratio at the inlet of 0.21 and air / propane of 0.24, respectively (zero experiment is comparative). ;
The results of the experiments are presented in table-2.
FIG. 3 illustrates the effect of the recycling of 2-nitropropane on the composition of the nitroparaffins obtained.
The mass ratio in grams of recycled 2-nitropropane to the number of moles of the Injected propane is applied on the abscissa axis - 2NP, g / mol 0 CjHg, the mass of each nitroparaffin (M,%) is plotted on the ordinate axis. Curves 1–4 correspond to the preparation of nitromethane, 2-nitropropane, 1-nitropropane, and nitrostan, respectively. Curve 5, which shows an increase in the total amount of nitro. Paraffins, depending on the amount of recycled 2-nitropropane, has a maximum. At this point, for the same amount of injected propane, the maximum capacity is obtained for the aggregate nitroparaffins and, therefore, the minimum installation size.
FIG. 4 refers to the specific consumption (kg / kg produced by the Fin Nitropara) in the framework of the propane nitration reaction carried out at H40c for a propane / nitrodioxide ratio of 5 mol and air / nitrodioxide 1.8.
The specific consumption of propane and nitrodioxide is deposited on the ordinate axis, and the mass ratio of recycled 2-nitropropane / mole of introduced propane (2-NP, t / mol) is on the axis
Uh
abscissa. Curve 1 corresponds to propane, and curve .2 corresponds to nitrodioxwd.
The curves in FIG. 4 shows that the consumption of nitrodioxide and propane decreases when recycling 2-nitropropane, and the consumption is the smaller, the greater the amount of 2-nitropropane.
Froze Nitration of ethane / propane mixtures.
A series of experiments was carried out on the propane nitration in the presence of ethane at 320 - 340 ° C, a pressure of 10 bar, a contact time of 5.5 s, and the ratio of N0- / hydrocarbons at the reactor inlet is designated СН, С (zero experience is comparative).
The test results are presented in Table. 3
FIG. 5 shows the change in mass of the various nitroparas obtained. Finov and the change in the total mass depending on the ratio of ethane / propane in the nitrate mixture. The mass in grams for each nitroparaffin is plotted on the ordinate axis (NPF), and the total mass of the resulting nitroparaffins in grams is plotted on the abscissa axis. Curves 1 - A correspond to 2-nitropropane, nitromethane, 1-nitropropane and nitroethane, respectively. Curve 5 corresponds to the change in the total mass of the product in grams.
FIG. 6 shows the change in the specific consumption (kg per kg of the obtained nitroparaffins) depending on the ethane / propane ratio at the reactor inlet. Unit costs (kg / kg) are plotted on the y-axis, and the amount of ethane introduced (%) is on the x-axis.
Curves 1-4 correspond to the specific consumption of propane, ethane, a mixture of ethane - propane and nitrodioxide.
From tab. 3 and FIG. 5 and 6 it follows that the amount of ethane introduced into the nitrate mixture can control the composition of nitroparaffin products.
99198.4
The effect of the amount of recycled 2-nitropropane on the ratio of nitroparaffins produced and the consumption of nitrodioxide, propane and this, is not shown in the table. four.
FIG. 7 shows the spectrum of the obtained nitroparaffins.
The content of each nitroparaffin is indicated on the ordinate, and the temperature on the abscissa.
FIG. 8 shows the specific consumption of reagents (kg per kg of all nitroparaffins obtained) according to the reactions carried out at the temperature of 15 indicated in table. 4. The consumption of reagents is shown on the y-axis, and the temperature is shown on the abscis axis.
In tab. 5 shows the effect of reaction conditions (in particular, temperature 2Q ry) on the behavior of recycled nitroparaffins.
The effect of pressure on the reaction time is shown in Table. 6
The reduction of pressure at a constant other reaction parameters leads to an increase in competing oxidation reactions, at which the specific consumption is more significant.
To create favorable conditions for nitration, a decrease in
30, the contact time and the air / propane ratio are reduced: under these conditions, the reaction is noticeably improved in terms of consumption, however, the ratio of nitro35 paraffins is worsened from the point of view of nitromethane.
Thus, temperature values of 275, 290, 305, 320, 330, 340, 360, AOO, and pressure values of 10, 20, 30, 40, and 60 bar are confirmed by examples.
The amount of recycled 2-nitropropane is 13, 47, 86 and 120% of that obtained.
Table 1
340340
77
1010
0,210,2i clothes
0.2380.238 e
O0,070
The continuation of the table.1.
340340 7 7
1010 0.21 0.21 0.240 0.240 0.056 0.05
2-Nitropropane 1 - Nitropropane
WITH,
Indicators
340 5.5
340 5.5 10 10
0.21 0.20 0.3238 0.053 01
34.529.7 6.1 17.6 an
46.638 en 12.8 14.7
0.17 0.32
1.95 0.49 1.27 0.9
29
eight
32.2
35 16.8
eight
17
16 1.42
0.82
1.83
1.42 1.070 K 28 0.80 0.70
Table 3
340340320340320
5.5 5.55.55.5 5.5
1010101010
0.20 0.200,200.20 0.20
0,048 0,0500,0500,050 0,050
1j02 4
31,534,027,031,726,5
17,723,525,435,537,3
3932,537,224,528,5
12.810.010.38.3 7.6 0.68 0.600.450, 0.85 0.59 0.450.390.11 0.36 1.27 1.05.840.43 1.21
1.18 1.41 0.89 1.37 1.12 iizzirrnziLiz:
Table 4
eleven
2-NP / S, mole / / 100 g-n obtained NPF
NM per 100 g / atom
entered
hydrocarbon
Ne
2-NP
1-NP
Costs, kg / kg of nitroparaffins obtained;
С, Н8 СгНб NO / CjHj, (weight) at the entrance to the reactor 0.21 0.23 Air / CgHg (weight) at the entrance to the reactor 0,238 0,217 The composition of the mixture obtained.%: 34.5 37.2
119919812
Continuation of table.5
0.20
0.24
0.21
1, A7
1.24 1.08 0.61
Table 6 0.23 0.25 0.27 0.25 0.22 0.153 0.142 0.125 38.4 27.4 25.3 19.8
13 Costs kg / kg NOj 3.95 NPFs obtained Organic phase / water phase (by weight) 1.07
. NP9, g
SO
280
14
I 199198 Continuation of table.6.
VG
Jw
Figure 1 3.20 3.92 1.74 1.42 1.07 0.64 0.35 1.22 1.32 1.4
4k
.fl
V

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t4t.t
D% 1 w
S me.r / imC
t4
t
V4
t

w
, J
t.t
wl

"five

at
bv
wV (M
i; 4 "HM1: g yy;
i
W
TG .7
five
/
/
Z
#)
/;

/
Have
.
{YU
tfffO FIG. at
500 T,

权利要求:
Claims (2)
[1]
1. METHOD FOR PRODUCING NITROPARAFINS by nitration of propane or an ethane-propane mixture with nitrogen dioxide in a gaseous phase under a pressure of 10-60 bar in the presence of an oxygen-containing or inert gas at 275-460 ° C, characterized in that, in order to increase the content in the target product of nitromethane , the process is carried out in the presence of 2-nitropropane recycled after separation of the reaction streams.
[2]
, 2. The method according to π. 1, characterized in that the amount of recycled 2-nitropropane is 13-120% of the amount of nitro products obtained, and recycling is carried out in relation to the total mass of the obtained nitroparaffins, sequentially alternating with the production of nitroparaffins.

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引用文献:

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公开号 | 申请日 | 公开日 | 申请人 | 专利标题

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DE1037438B|1955-07-28|1958-08-28|Huels Chemische Werke Ag|Process for the nitration of aliphatic hydrocarbons and their halogen derivatives|

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US3113975A|1959-11-13|1963-12-10|Purdue Research Foundation|Vapor phase nitration of aliphatic hydrocarbons in the presence of ozone|

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US3133123A|1961-02-16|1964-05-12|Allied Chem|Vapor phase nitration of cyclohexane|

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BE790694A|1971-10-29|1973-04-27|Azote & Prod Chim|NITROPARAFFINS MANUFACTURING PROCESS|

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US3869253A|1972-10-19|1975-03-04|Azote & Prod Chim|Apparatus for producing nitroparaffins|FR2442828B1|1978-11-14|1981-07-24|Azote & Prod Chim|

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FR2452315B1|1979-03-28|1985-07-05|Azote & Prod Chim|NITRATION REACTOR FOR HYDROCARBONS IN GAS PHASE UNDER PRESSURE|

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FR2453846A1|1979-04-10|1980-11-07|Azote & Prod Chim|PROCESS AND PLANT FOR MANUFACTURING NITROPARAFFINS BY NITRATION OF HYDROCARBONS IN THE GASEOUS PHASE|

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US4458094A|1982-01-22|1984-07-03|W. R. Grace & Co.|Process for forming nitroparaffin|

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US4524226A|1983-07-05|1985-06-18|W. R. Grace & Co.|Preparation of nitro compounds by vapor phase nitration of aldehydes|

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US4476336A|1983-07-05|1984-10-09|W. R. Grace & Co.|Process for forming nitroparaffin|

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EP0146203A3|1983-12-19|1986-03-12|W.R. Grace & Co.-Conn.|Preparation of nitro compounds by vapor phase nitration of oxygenated hydrocarbons|

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US4517392A|1983-07-05|1985-05-14|W. R. Grace & Co.|Preparation of nitro compounds by vapor phase nitration of organic alcohols|

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US4517393A|1983-07-05|1985-05-14|W. R. Grace & Co.|Preparation of nitro compounds by vapor phase nitration of ketones|

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US4517394A|1983-07-05|1985-05-14|W. R. Grace & Co.|Preparation of nitro compounds by vapor phase nitration of carboxylic acids|

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FR2558827B1|1984-01-27|1986-06-27|Azote & Prod Chim|PROCESS FOR THE MANUFACTURE OF NITROMETHANE AND INSTALLATION|

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US4766257A|1984-09-12|1988-08-23|W. R. Grace & Co.|Preparation of nitro compounds by vapor phase nitration of olefins|

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FR2632635B1|1988-06-09|1990-10-19|Seppic Sa|PROCESS FOR THE MANUFACTURE OF NITROMETHANE|

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法律状态:

优先权:

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申请号 | 申请日 | 专利标题

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FR7809837A|FR2421867B1|1978-04-04|1978-04-04|

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