JPH03206053A - Production of 2-halo-1-alkene - Google Patents

Abstract

PURPOSE:To produce the subject compound by reacting 1,2-diene,1-alkyne or a mixture thereof with a hydrogen halide in the presence of an activated alumina containing < a specified ratio of Na2O or a material prepared by supporting copper, etc., thereon as a catalyst. CONSTITUTION:In a reaction between a compound of formula I or II (R<1> and R<2> are H, alkyl, cycloalkyl or aryl) or hydrocarbons containing a mixture thereof and a hydrogen halide for production of the subject compound, the above mentioned reaction is carried out in the presence of an activated alumina containing <0.1wt.% Na2O or a material (preferably Cu-Ce/gamma-alumina) prepared by supporting copper and/or a rare earth lanthanum-based metal thereon as a catalyst at 220-330 deg.C and atmospheric pressure-10Kg/cm<2>G. By the above- mentioned method, the objective substance can be obtained with a high conversion and a high selectivity. When carrying out the reaction in an anhydrous system, corrosion of an apparatus can be prevented and the lifetime of the catalyst can be prolonged.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to an efficient method for producing 2-halo-l-alkenes useful as raw materials for methyl methacrylate (MMA). -hydrocarbons such as dienes, 1-alkynes, and hydrogen halides using a specific catalyst,
In particular, by conducting the reaction in an anhydrous system, 2-halo-1
- Concerning a method by which alkenes can be produced.

[Prior Art and Problems to be Solved by the Invention] Methyl methacrylate (MMA) has excellent transparency and weather resistance, and is extremely useful as a molding material. MMA is manufactured worldwide using the acetone cyanohydrin (ACH) method, which uses acetone and hydrocyanic acid, but there are problems such as unreliable supply of the raw material hydrocyanic acid and disposal of by-product ammonium sulfate. An alternative method is desired.

As a method to solve such problems, 1,2-diene. Terminal acetylene or mixture thereof (MAPD)
A method for producing 2-halo-1-alkenes from gas has been proposed (Japanese Unexamined Patent Publication No. 61-97233). This method uses carbon or alumina, especially alumina, as a catalyst and furthermore uses at least 1,000 p of carbon during the reaction.
It is characterized by the presence of ps+ water, and it is stated that this can reduce the deactivation rate of the catalyst. However, when the present inventors tried this method again and examined the results, they found that the presence of water resulted in: (1) corrosion of reactor I by hydrochloric acid, (2) decrease in 2-chloropropene selectivity due to by-produced acetone, and (2) The problem became clear that the conversion rate decreased and (1) the deactivation rate actually increased.

[Means to solve the problem]

In order to solve these problems, the present inventors conducted extensive research and found that by using a specific catalyst, 2-halo-l-alkenes can be produced even in anhydrous systems without the risk of equipment corrosion. High conversion rate. It was discovered that it can be produced stably with high selectivity, and based on this knowledge, the present invention was completed.

That is, the present invention provides the general formula C}I2=C}l R1(
In the formula, R1 represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group. ), 1-alkyne represented by the general formula CH=C-CHZR'' (wherein RZ is a hydrogen atom, and represents an alkyl group, cycloalkyl group, or aryl group), or a mixture thereof. In producing 2-halo-1-alkene by reacting a hydrocarbon containing hydrogen with a hydrogen halide,
A method for producing 2-halo-1-alkenes, characterized in that an activated alkali with a Na2O content of less than 0.1% by weight or a support of copper and/or a rare earth lanthanum metal is used as a catalyst. It provides:

In the present invention, a hydrocarbon containing 1,2-diene, l-alkyne, or a mixture thereof as described above is reacted with hydrogen halide (HX) to produce 2-halo-l-alkene. The reaction formula is as follows.

X ■ CHz = C = CHR' + HX → C
Ht=C CHzR'X 5co=c CHJ" +HX C}I2
The hydrocarbon used as a raw material in the present invention is represented by the general formula CH!=C=CHRI as described above.
．． 2-diene, 1-alkyne represented by the general formula CHEC CHtR" is the active species, but it is a mixture containing saturated alkanes, alkenes, dienes and alkynes, as well as small amounts of aliphatic compounds having 2.4.5 carbon atoms. But it's okay.

Here, pi of the above general formula. nt represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group, and preferably an alkyl group having 1 to 10 carbon atoms or a hydrogen atom. More preferably, Rl and Rt are each a hydrogen atom, and therefore, the 1,2-diene used in the present invention is preferably propadiene (PD
), and the 1-alkyne used in the present invention is preferably brobin (methylacetylene (MA)). In the present invention, the above-mentioned 1,2-diene, 1-alkyne or a mixture thereof (hereinafter abbreviated as MAPD) is used.
) is used as a raw material, but MAPD in the raw material
: The degree of a is preferably 65% or less; if it exceeds this, the risk of explosion increases, so caution is required. Next, hydrogen halide (HX), which is the other raw material in the present invention, includes hydrogen bromide, hydrogen chloride, hydrogen iodide, and hydrogen fluoride. Among them, hydrogen chloride and hydrogen bromide are preferable, and especially hydrogen chloride Hydrogen is preferred.

In the present invention, when producing 2-halo-1-alkenes using these raw materials, low-soda activated alumina or copper and/or rare earth lanthanum metals (lanthanum, cerium, etc.) supported thereon are used as catalysts. It is characterized by the use of objects.

Here, the activated alumina needs to have a low soda content, more specifically, it needs to have a Na2O content of less than 0.1% by weight, but in particular, γ-alumina with a high specific surface area has high activity It is preferred because it shows high selectivity.

Further, the metal-supported T-alumina may be used with copper alone, or may be supported with rare earth lanthanum metals (lanthanum, cerium, etc.).

In the method of the present invention, Cu-Ce/r-alumina, which is a combination of copper (Cu) and cerium (Ce), is particularly preferably used because it improves selectivity and catalyst life.

Cu in such a Cu-Ce/y-alumina catalyst
Although there is no particular restriction on the mixing ratio of metals such as Ce and Ce, the Cu/Ce atomic ratio is preferably 1 or more, and most preferably 1 to 3. In addition, the supported amount of metals such as Cu and Ce is
The amount is 0.1 to 50% by weight, preferably 2 to 40% by weight, and more preferably 5 to 20% by weight based on the activated alumina.

Note that Ce forms a solid solution with Cu and is considered to have the effect of suppressing the scattering of Cu in an HCffi atmosphere.

In the present invention, active species (MAPD) in hydrocarbons are subjected to a halogenation reaction using the above-mentioned catalyst, and the reaction can be carried out in a liquid phase or a gas phase, and it is particularly preferable to carry out the reaction in a gas phase.

It is preferable to carry out the reaction under the following conditions. First, regarding the reaction pressure, the reaction can be carried out under reduced pressure, atmospheric pressure, or increased pressure; however, although the reaction rate can be increased under increased pressure, there is a greater risk of explosion, so care must be taken. The reaction pressure is usually atmospheric pressure to 10 kg/
It is preferable to use cdG. Furthermore, the reaction can be carried out over a wide range of temperatures from 100 to 400°C, but the preferred reaction temperature is 200°C.
~360°C. At low temperatures below 200°C, 2-
This is not preferable because the bioactivity of chloropropane and 1-chloropropene becomes significant and the selectivity of the target 2-chloropropene decreases. Furthermore, at temperatures above 360"C, the activity of the catalyst decreases significantly due to coking, and 1-
In addition to chlorobropene, saturated and unsaturated compounds with 4 carbon atoms.
This is undesirable because the viability of unknown components becomes noticeable and the selectivity of the target product decreases. The optimum temperature range is 220 to 330° C. In this range, high conversion and high selectivity can be obtained, and the reaction can be carried out stably.

Furthermore, the water concentration during the reaction should be as low as possible, and the reaction is preferably carried out in an anhydrous system. By lowering the water concentration, ■ Corrosion of equipment due to hydrochloric acid, ■ Decrease in 2-chloropropene selectivity due to by-produced acetone, ■ MA
It is preferable to carry out the reaction in an anhydrous system because problems such as a decrease in PD conversion are resolved, and (1) the deactivation rate of the catalyst is rather reduced. In addition, the raw material hydrogen halide (HX) is
Any ratio can be added to the active species (MAPD) in the hydrocarbon, and the OX/MAPD molar ratio is not particularly limited, but preferably 1 mole of the active species MA
Hydrogen halide (FIX) is 0.4 to 2 mol per PD. At a low molar ratio of hydrogen halide (OX), the conversion rate of the active species MAPD is low, while at an excess, the halogenation of propylene present in the hydrocarbon results in 2-chloropropane, −
Butyl chloride. This is not preferable because the effects of chlorides having 5 and 6 carbon atoms become noticeable and the selectivity of the target 2-halo-1-alkene decreases.

Furthermore, the most preferable Hχ/MAPD molar ratio is 0.8
-1.2, and within this range, the desired purpose can be achieved with a high conversion rate and high selectivity.

The usage amount of the catalyst used in the reaction in the present invention - FMAPD (catalyst weight/MAPD supply amount; g-cat-sin/mo
l) is not particularly limited and can react with any amount of active species in hydrocarbons, but
W/F is 2~80 (XIO” g-cat-sin
/mol). If the amount of catalyst used relative to the active species is small, the conversion rate will be low, while if the amount of catalyst used is large, the conversion rate will be low, whereas if the amount of catalyst used is large, the production of saturated, unsaturated, and unknown components of carbon atoms from propylene present in the hydrocarbon will be reduced. This is undesirable because the effect becomes noticeable and the selectivity of the target object decreases. The most preferable range of -/F in the present invention is 5 to 5
0 (X 10' g-cat-win/mol), and the conversion rate is high in this range. The desired 2-halo-1-alkene can be produced stably with high selectivity.

Note that although the catalyst is deactivated over time due to coking, this can be easily regenerated by a known method, for example, by passing air through the catalyst layer at a high temperature for several hours.

The regeneration of this catalyst is preferably between 350 and 550'
C for 2 to 24 hours using an oxygen-containing gas. Note that at this time, water may be added to perform regeneration.

The 2-halo-1-alkene produced as above is
It can be separated by conventional methods, and can be carboxylated and further esterified to produce an acrylate ester.

〔Example〕

Next, the present invention will be explained in detail with reference to examples.

In addition, in the following Examples and Comparative Examples, MAPD gas having the following composition was used as the raw material hydrocarbon.

Serum mol χ Broban 4.7 Brobylene 69.2 Cyclopropane 0.7 Probadiene (PD) 92O Methylacetylene (Group A) 16.5 (Active MAPD 2
5.5) 020 concentration 55wt ppm Also,
HCl gas manufactured by Steel Gas Chemical Co., Ltd. (purity of 99.9% or more) was used. In addition, for anhydrous reactions, the above MAPD
The gas was passed through a molecular sieve 3A to dehydrate it before use.

Examples 1 and 2 and Comparative Example 1.2 Using an atmospheric pressure fixed bed flow reactor (made of quartz) with an inner diameter of 20 mmφ and a length of 400 mm, γ- shown in Table 1 was used as a catalyst.
This was carried out using an alkuna catalyst.

The above atmospheric pressure fixed bed flow reactor was first filled with a filler (quartz wool), then a predetermined amount of catalyst shown in Table 1, and pretreated (nitrogen gas flow rate: 200 d/mj).
n, 300°C, 2 hours).

Next, after lowering the temperature to 200°C, the nitrogen supply was stopped and the H2O
900ppm. Hydrocarbon 6 0. 6 Ncc/
sin. HC I! 1 4. 7Ncc/min,
HCj! /MAPD molar ratio=0. 9 5 under the conditions shown in Table 1, MAPD gas and HCI! ．．
were each introduced into the reactor from a cylinder through a mass flow meter, and the reaction was started at 200°C.

The flow rate of the MAPD gas was controlled using two lines of mass flow meters: a line for introducing it as is and a line for passing through the water bottle 1, thereby controlling the concentration of fl2O in the raw material gas. After conditioning for 30 minutes, samples were taken after 1 hour of reaction. Thereafter, the temperature was raised to 250°C in 30 minutes, and after one hour the temperature was stabilized, samples were taken again.

In this way, the reaction was carried out sequentially up to a reaction temperature of 300''C, and sampling was carried out at reaction temperatures of 200''C, 250'C, 270°C and 300''C, and the conversion rate and selectivity at these temperatures were measured. The results are shown in Table 1.

According to Table 1, the following can be seen.

That is, from Example 1 and Comparative Example 1, when we look at the γ-aluminum ξna catalysts having almost the same specific surface area (approximately 310 nf/g), we find that the Na2O content in the T-aluminum ξna catalyst is 0. 1% by weight of ungrooved ones compared to those without grooves.
It can be seen that the activity and selectivity are increased.

This was found to be the same when comparing Example 2 and Comparative Example 2, which were conducted using a γ-alumina catalyst having a low specific surface area.

Examples 3 to 5 Using a normal pressure fixed bed flow reactor with an inner diameter of 10 mmφ, γ-alkuna (manufactured by Sumitomo Chemical Co., Ltd., NKH3-
2 4) Using 12Og, W/F=0.68xlO'
g-min/mol, and in an anhydrous H2O system (Example 3), n2O55ppra (Example 4)
Alternatively, Ht01 1,000ppm (Example 5
), except that the reaction was carried out in the same manner as in Example 1.

The results are shown in Tables 2-4.

Table 2 Anhydrous system (Example 3) Table 3 Hz0 55pp garden (Example 4) Table 4 H20 112O00ppm (Example 5) From Tables 2 to 4, by lowering the water concentration, M
It can be seen that the APD conversion rate and selectivity are increased. Note that the improvement in selectivity is due to the reduction of acetone and 2-chloropropane as by-products.

Examples 6 and 7 (Temporal Change Test) Using an atmospheric pressure fixed bed flow reactor with an inner diameter of 10 mmφ and a length of 400 m, γ-aluminum (N) shown in Table 1 was used as a catalyst.
KH3-24. Sized to 16-28 mesh. The test was carried out using 1.8 g of Sumitomo Chemical Co., Ltd.).

The above atmospheric pressure fixed bed flow reactor was first filled with a filler (quartz wool), then the above catalyst, and pretreated (nitrogen gas flow rate: 200 d/a+in, 300 d/a+in).
°C, 2 hours).

Next, the temperature was lowered to 200°C, the nitrogen supply was stopped, and the hydrocarbon 13. 4 Ncc/-in, HCj! 3. 2
Ncc/win, W/F-1.2X10'g-cat
・win/mol. Hcj! /MAPD mono ratio = 0
．． 95 and the concentration of water in Table 5, MAPD
Gas and HCffi were each introduced into the reactor from a cylinder through a mass flow meter, and the reaction was started at 200°C. The flow rate of the MAPD gas was controlled using two lines of mass flow meters, one for direct introduction and the other for the line passing through the water pot. The temperature was raised to 300°C in 30 minutes and sampled 1 hour after it stabilized.

Continuous operation was performed in this state for 4 days. During this period, analysis of the living matter was carried out every 1 to 4 hours. Conversion rate, selectivity and degradation rate were measured after 3 hours and 96 hours. The results are shown in Table 5.

Table 5 From Table 5, by lowering the water concentration,
Similar to Table 4, it can be seen that as the MAPD conversion rate and selectivity increase, and as the HCl conversion rate increases, the deterioration rate actually decreases. Note that the improvement in selectivity is due to the reduction of by-products acetone and 2-chlorobroban.

Examples 8 to 10 In Example 1, except for the conditions shown in Table 6, Example 1
The reaction was carried out in the same manner. The results are shown in Table 6.

Table 6 From Table 6, HC Ve/? It can be seen that as the lAPD molar ratio increases, the conversion improves, but the selectivity decreases rapidly when the molar ratio is 1.5 and HCl is in excess. Example 11 In Example 1, an atmospheric pressure fixed bed flow reactor with an inner diameter of 10 mφ and a length of 400 mm was used, and it was an anhydrous system with a catalyst amount of 3.2 g and a hydrocarbon of 1.3. 4 Nc
c/win. HCl 3. 2 Ncc/sin.
W/F=2. I X10'g-cat-sin/m
The reaction was carried out in the same manner as in Example 1, except that the reaction was carried out under the conditions of 330''C.The results are shown in Table 7.

Table 7 (Example 11) The above Table 7 (Example 11) and the above Table 2 (Example 3)
Comparing with, what happens when the W/F becomes larger? It can be seen that although the IAPD conversion rate increases, the selectivity of 2-chlorobropene decreases, especially at high temperatures of 300''C or higher. In addition to using a fixed bed flow reactor, as a catalyst,
Two types of Cu-Ce/1-alumina catalysts (RC-11, RC-20) prepared by the following method and γ-Alξ
catalyst (NKH 3-24, manufactured by Sumitomo Chemical Co., Ltd.) (all catalyst particle sizes are 16 to 28 mesh) and 1.5
g, hydrocarbon 1 3. 4 Ncc/+sin. H
Cj! 3. 2Ncc/sin, and the Cu/Ce ratio and HtO concentration shown in Table 8.
The reaction was carried out in the same manner. The results are shown in Table 8. Cu-Ce-Aluminum RC-11)
CuCIl12To0 1. 3 4 g and Ce
Cj! i4Hg0 2. 9 7g and distilled water 9
T-aluminum ξna catalyst (manufactured by Sumitomo Chemical Co., Ltd., NKH3-
24) After being impregnated with 102Og for 1 hour, 110℃
was dried for 2 hours to obtain a Cu-Ce supported γ-alumina catalyst. The metal content in this catalyst is Cu3. Owt%, Ce6.
It was 81 t%. Cu-Ce-AlQ RC-2
0) In the preparation of RC-11, CuCj! ,2
Hz0 1. 3 4g and CeCj! 17Ht0
2. Instead of 9 7 g, CuCIg・2Hz
0 4.6 5 g and CeCl34Fh0 1
A Cu-Co supported T-aluminum ξna catalyst was obtained in the same manner as in the preparation of RC-11, except that 0.42 g was used. The metal content in this catalyst is Cu7.1wt%, Cel6
．． It was 61 t%. Table 8 From Table 8, the following can be seen.

That is, compared to Example 13 (water concentration 900 ppm), Example 12 (water concentration 55 ppm) with a lower water concentration has MAPD similar to the T-alumina catalyst.
It can be seen that the conversion rate and selectivity of 2-chloropene are increased.

In addition, while the Cu/Ce molar ratio was 1, the supported amount was 2.
By doubling the amount, compared to Example 13, Example 14 shows a decrease in MAPD conversion and an improvement in 2-chloropropene selectivity.

Examples 16 and 17 (temporal change test) Inner diameter 10 plates φ
, using an atmospheric pressure fixed bed flow reactor with a length of 400 m, and using the T alumina catalyst shown in Table 9 (Sumitomo Chemical Co., Ltd.) as the catalyst.
The test was carried out using 1.8 g each of Cu-Ce/7-aluminum catalyst (R(,-11)) and Cu-Ce/7-alumina catalyst (R(,-11)).

The above atmospheric pressure fixed bed flow reactor was first filled with a filler (quartz wool), then the above catalyst, and pretreated (nitrogen gas flow rate: 200 Idl/min, 30
0°C for 2 hours).

Next, after lowering the temperature to 200″C, nitrogen was stopped, and hydrocarbon 13.4 Ncc/win, HC 13.2
Ncc/win, W/F= 1.2 x 10'g-
cat-win/mol + HC A /MAPD molar ratio = 0. 95, and in an anhydrous system, MAPD gas and Il1 were each introduced into the reactor from a cylinder through a mass flow meter, and the reaction was started at 200"C.Then, the temperature was raised to 300"C in 30 minutes and stabilized. Samples were taken 1 hour later.

Continuous operation was performed in this state for 8 days. During this period, product analysis was performed every 1 to 4 hours. The conversion rate, selectivity and deterioration rate were measured after 3 hours and 192 hours. The results are shown in Table 9.

Table 9 According to the above Table 9 and the above Table 8, when comparing Example 12 and Example 15, and Example 16 and Example 17, it is found that Cu-Ce is supported on γ-alumina. It can be seen that the selectivity is improved, especially at 330°C.

On the other hand, the activity improves at low temperatures (200-250°C), but decreases at higher temperatures.

It is also found that the life of the catalyst is improved and the production of very small amounts of liquid biological substances is suppressed.

Comparative Examples 3 to 9 In Example 1, an atmospheric pressure fixed bed flow reactor with an inner diameter of 10 mm and a length of 400 mm was used, and the following catalysts (sized to 16 to 28 mesh) were used as catalysts. Use 5g and 1 hydrocarbon 3. 4 Ncc/+
in and HC 1 3. The reaction was carried out in the same manner as in Example 1, except that the reaction was carried out under the conditions of 2 Ncc/lIlin. The results are shown in Table 10.

Ichitoku-14 One Person One Silica Activated Carbon Mordenite HL Type Zeolite HY Type Zeolite NaY Type Zeolite HZSM-5 ? - Car Mizusawa Chemical Industry■. SILBEAD-SB Taihei Kagaku Sangyo, Brokol CM Tosoh ■, TSZ-6408 Tosoh ■, TSZ-500 H Catalyst Kakai Kogyo ■ Catalyst Or Kogyo ■ ZCP-50 Prototype (SiO ■ / A I. zo: + ratio 300) 1st
According to Table 0, the above catalyst is a T-alumina catalyst or a C
Compared to the u-Ce/T-alumina catalyst, the conversion rate and selectivity are low, especially the conversion rate is extremely low, and the activity is inferior.

Moreover, from the above-mentioned Examples 1 to 5 and Examples 8 to 15, both the conversion rate and the selectivity are low at 200″C or less;
Although there is no significant difference in the conversion rate and selectivity at ~300°C, it can be seen that the conversion rate and selectivity decrease at 330°C.

: Effect of the invention] According to the production method of the present invention, 2-halo-1-alkene useful as a raw material for methyl methacrylate can be stably obtained at a high conversion rate and high selectivity.

Moreover, according to the production method of the present invention, since the reaction can be carried out in an anhydrous system, corrosion of the equipment can be prevented.
Furthermore, the life of the catalyst can be extended.

Claims (1)

[Claims] (1) 1,2-diene represented by the general formula CH_2=CH-R^1 (wherein R^1 represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group), a general formula CH≡C -CH_2R^2 (in the formula, R^2 is a hydrogen atom,
Indicates an alkyl group, a cycloalkyl group, or an aryl group. ) is reacted with a hydrocarbon containing a 1-alkyne or a mixture thereof with a hydrogen halide to produce 2.
- In the production of halo-1-alkenes, activated alumina with an Na_2O content of less than 0.1% by weight or activated alumina with copper and/or rare earth lanthanum metals supported thereon is used as a catalyst. -Hello-1-
Method for producing alkenes.