SU923587A1 - Catalyst for dehydrochlorination of 3,4-dichlorobutene-1 - Google Patents

Description

(St) CATALYST FOR DEHYDROCHLORINE 3,4-DICHLOROBUTENE-1

The invention relates to the production of catalysts for the process of dehydrohalogenating chlorine substituted hydrocarbons and the production of 2-chloro 6-butadiene-1. 3. The closest to the present invention is a catalyst for the dehydrohalogenation of chlorine derivatives of hydrocarbons containing 2-6 halogen atoms, containing 1-10 wtL of oxides of rare-earth elements (La, Ce, Nd Vd, 1 / b) and the carrier is alumina. The depth of conversion of the feedstock at 590 ° C is 22–30 wt.%. The process is complicated by significant losses and coke formation (6–9 wt.) Lj. A disadvantage of the known catalyst is the low activity of the depth of conversion of the feedstock at 590 °. The purpose of the invention is to increase the activity of the catalyst. This goal is achieved by a catalyst of the composition described, containing 0.2-1.5 wt. compounds of the rare-earth element, in which the catalyst contains a metal complex compound — lanthanide tris- (3 methoxybenzoate) of the formula (OCH3) COOj3, where Me is lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, lutetium, and the carrier is cGyumuminium oxide. . The catalyst according to the invention has a high activity — with a conversion depth of 3, -Dichloro-100-1100, a temperature of 110-150 ° C and atmospheric pressure, the yield of chloroprene is 58-61 -weight. The catalyst is prepared by impregnation (with an appropriate solution of the complex. Alumina oxide (granulation of 0.25-0.5 mm) is preliminarily calcined in a current of air for C h at 600 C. Example 1.10 g of Jf-A, 0 hall, 37.7 ml of 0.0027 N solution of Ce CgH / {OCH j) C007j (0.02 g), incubated at room temperature until it removes moisture (h). But then the catalyst is dried at 120 ° C for 6 hours in a drying oven. Thus prepared, the catalyst contains 0.21, (OCH) COO / 5 and the rest of the carrier. Example 2. 10 g (the hall is covered with 155 ml of a 0.0028 N solution of Ce | CgH (OCH) COOj3 (0.08 g), kept at room temperature (h). Then the catalyst is dried at 120 ° C for 6 h. Prepared Thus, the catalyst contains 0.8 Ce CgHy {OCH) COOjj and the support is the rest. g (0 room Example 3, wooed 210 ml of 0.0027 solution of 10 g is poured; 126 ml of 0.0033 N solution 126 ml of 0, i) 033 N solution of 109.5 ml of 0.0037 N solution of 102.5 ml of 0.004 N solution 102.5 ml of Q, 00k N solution 91, ml 0, N solution 91 ml 0, N solution

The operations of Example 1 are then repeated. .

Catalysts so prepared contain 0.8 complex compounds by weight of carrier.

(

The process is carried out at atmospheric pressure in a laboratory setup with a pulsed feed. A catalyst is loaded into a tubular type reactor made of molybdenum glass, kept for an hour in a stream of inert gas (gels) at 200 ° C, and the raw material is fed to the evaporator with a syringe (evaporator temperature is 150 ° C). The analysis of the reaction products is carried out by gas chromatography at 60 ° C on a steel stuffed column 3 m long and 3 mm in diameter with a thermal conductivity detector. As the stationary phase, 7% polyethylene glycol 1500 (PEG-1500) is used + 7% of Apiezon L applied on Inze brick, calcined at 1200 C.

Example 6. The catalyst in the amount of 0.25 g is loaded into the reactor. After activation (1 h in a current of helium, 200 s), the temperature is reduced to the set point (110, 130, 150 ° С). The starting material 3, -dichlorobutene-1 (1, 157-10-g) is fed to the evaporator. Weighing feed rate 4.6310 g / g catalyst (contact time 0.77 s).

In tab. Figure 1 shows the results of the dehydrochlorination of 3, -dichlorobutene-1 on catalysts with different contents of the complex on the support. The test was carried out at IBOC, catalyst loading of 0.25 g (contact time 0.77 s), feed 3, -Dichlorobutene-1 1.157.10-g. 8 Ce C6Hv (OCHj) COOJ3 (OJI g), vydergz (0.11 live at room temperature until moisture is completely removed (h). Then the catalyst is dried at 120 ° C for 6 hours. The catalyst thus prepared contains 1.1% Ce jCgH (OCHN) COO.z and the carrier rest. Example 4. 10 g are poured with 287 ml of 0.0027 N solution of Ce | C5Nu (OCH) C007z (0.15 g), kept at room temperature until moisture is removed (h). Then the catalyst is dried for 6 hours, the catalyst prepared in this way contains 1.5% (OCH) COOj and the carrier is the rest. Example 5. Similarly, catalysts are prepared based on compounds of lanthanum, praseodymium, neodymium, samarium, gadolinium, and luteum C5Hi (OCH3) COOJ3 (COSN) COO sulfur (CESN) CABu (CESN) beHv (OCHj) COOj3: CPSH (OCH) (0.08 g) Cg N ( OCHj) COOj3

As a result of studying the catalytic activity of samples containing 0.2-1.5 wt.% Of a complex prepared on the basis of cerium, it was established that 20 at a 100% conversion depth of the feedstock, the highest degree of conversion is 3, -Dichlorobutene-1 in 2- chlorbutadiene-1,3 is observed at a complex content of 0.8%.

Table 1

In tab. Figure 2 shows the result of testing a catalyst of optimal composition, containing 0.8% CefCgH (OCHj) COOj3 a at different process temperatures and the following conditions: catalyst loading 0.25 g; handout 3,

1.157 - 10 g; "-dichlorobutene-1 - 0.77 s.

table 2

A catalyst containing tris- (3 methoxybenzoate) lentanoid in an amount of 0.2-1.5 and alumina carrier for the 3-dichlorobutene-1 dehydrohalogenation reaction is characterized by increased activity, allows reducing the process temperature, reducing the content of rare-earth elements to 0, 2, completely eliminate the use of noble metals.

Claims (1)

1. US patent No. 3927131, cl. 260-65, published. 1975 (prototype).