Method of producing lower alkyl tert-butyl ethers

专利摘要:
1506461 Removing isobutene from hydrocarbon streams SNAMPROGETTI SpA 13 May 1975 [21 May 1974] 20210/75 Heading C5E [Also in Division C2] A process for selectively removing isobutene from a hydrocarbon stream comprises feeding a primary alcohol and a C 4 hydrocarbon stream comprising isobutene and buta-1,3-dene, where there is at least 4% by weight of buta-1,3-diene in the hydrocarbon stream, to a synthesis zone containing as catalyst an acid ion exchange resin, at a temperature in the range from 60‹ to 120‹ C., with a liquid hourly space velocity (expressed as the volume of liquid per hour and per volume of catalyst) in the range of from 5 to 35, and where the temperature in the synthesis zone is approximately in accordance with the following equation where T is the temperature expressed as ‹ C. and LHSV is the liquid hourly space velocity; and separating downstream of the synthesis zone the resulting alkyl tertiary butyl ether from other compound(s) present, by distillation. Reference has been directed by the Comptroller to Specification 1,176,620.
公开号:SU747415A3
申请号:SU752139259
申请日:1975-05-21
公开日:1980-07-23
发明作者:Анкиллотти Франческо；Пескаролло Эрманно；Масси Маури Марчелло
申请人:Снампрогетти С.П.А. (Фирма)；
IPC主号:

专利说明:

The invention relates to an improved process for the preparation of lower alkyl tert-butyl esters. A known method for producing lower alkyl tert-butyl ethers by reacting lower alcohols and isobutylene or isobutylene-containing fractions at a temperature of 0–200 ° C, a space velocity of 5–10 l / l catalyst i h in the presence of a cation exchange resin as a catalyst 1. In the case of using isobutylene containing fractions in a known manner, the latter must be purified from butadiene by extraction or selective hydrogenation, since acidic cation-exchange resins catalyze the dimerization and polymerization of dienes. However, these operations do not completely eliminate the loss of dienes and complicate the process, as a result of which the use of olefin-containing fractions with a high content (more than 2%) of dienes, for example, butadiene, is limited due to the need for their prior isolation. The aim of the invention is to control the process, the stated objective is achieved by a method of producing lower alkyl tert-butyl esters by reacting a lower alcohol with an isobutylene-containing fraction in the presence of a cation-exchange resin as a catalyst, the distinguishing feature of which is an butadiene from 2 to 40 wt.%, and the process is carried out at a temperature of 60-120 ° C, a space velocity of 5-35 l / l of catalyst, defined by the formula: V 1/2 T-25, where T is temperature, ° C . The process is advisable to conduct at a temperature of 60-80 ° C. The yield of the target product reaches 87%. Thus, compliance with these conditions allows you to control the secondary reactions of butadiene, which facilitates the selection of target products and allows the use of olefin fractions of steam cracking without prior treatment to remove butadiene. Example 1.150 g (cm) of olefin fraction C after steam cracking of the following composition, weight,%: propylene 6.03; isobutane O, 86; N-butane 3.73; butene-1 16.44; isobutylene 29.19; butei-2 - trans 5, 89; butene-2-cis 4.29; l, j-butadiene 39.57 is introduced into g into the vtoklav along with 20 g of methanol (-27 cm) {molar ratio of isobutylene; MtiTanol 1, 03) and as a catalyst; 12 g of Amberlite 15 are used (“-20 ci;
Mixes drink nag-reats up at silksm. Mixing. During this time: -: eki otoira.yut g: robes of the reaction mixture and analyze them, obtaining the results given in Table 1 about
Analysis results
L ....
The degree of conversion, weight. %
isobutylene
methanol
The yield of methyl-waste, butyl ether (MTBE) ,, weight, ° b
The degree of conversion, weight. %
butadiene
linear butenoB
The loss of butadiene is due to the formation of simple methylbutenyl zfir with small amounts of dimers (vinylcyclohexane) and co-measures.
75.01 79.82 75.10 71.54 77.62 87.69 92.26 93.25
79.09 87.27 81., 81 79.36
0.1 1.2 4.66 8.76 C, 1 0.1 0.1 0.1
As can be seen from example 1., in which the process is carried out continuously, a very long stay of ai; ia mixture in an autoclave contributes to the npcTsiKania secondary reactions of butadiene and negatively affects the degree of transformation of isorutylene; Under the conditions given in this example, the degree of predragenic isobutylene reaches a maximum of 60 minutes and then decreases.
This is due to the fact that MTBE, methanol and isobutyllen reach in a short period of time thermodynamic equilibrium and thereafter, despite the consumption of methane.g: a with the formation of butadiene adducts (simple bute :: Sludge esters), The system reacts along the path of the decomposition of MTBE and its components with the restoration of a state of equilibrium:.
Examples 2-4. The olefinosuc fraction of Example 1 is continuously reacted with methanol E by the presence of Amberlite 15 into the reactor with inhibited flow. The conditions for the conversion are given in Table 2.
Table
60
80
80
79.1
77.6 70.7 1.3 11.5
linear butenone 0.1 / 0.1 .0.1 MTBE yield, weight% 83.18 75.79 84.79
Based on the results of the experiments given in examples 2, 3 and 4, conducted in a continuous reactor with a slowed down flow, the same conclusions were drawn as in example 1. According to this method, a certain optimal velocity corresponds to a certain temperature, the higher value of which leads to to a higher degree of recovery
iutadiene, while lower than optimal, causes secondary reactions of butadiene and leads to a lower degree of isobutylene conversion.
Examples 5-7. Olefin stream obtained by steam cracking.
used in example 1, continuously in a flow reactor in the presence of Amberlite 15 is subjected to interaction with ethanol, propanol and butanol. Get the following results (see table 3)
Table 3.

权利要求:
Claims (2)
[1]
Claim
1. The method of producing lower alkyl tert.-Butyl esters by the reaction of a lower alcohol with an isobutylene-containing fraction in the presence of a cation exchange resin as a catalyst, characterized in that, in order to simplify the process, an isobutylene-containing fraction comprising butadiene from 2 to 40 weight is used %, and the process is conducted at a temperature of 60-120 ° C, a space velocity of 5-35 l / l of catalyst · h, determined by the formula: V = 1/2 T-25, where T is temperature, ° C
[2]
2. The method according to claim 1, characterized in that the process is conducted at a temperature of 60-80 ° C.

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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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IT23010/74A|IT1012687B|1974-05-21|1974-05-21|PROCEDURE FOR THE SYNTHESIS OF ETHES RI ALCYL TER BUTYL FROM A PRIMARY ALCOHOL AND ISOBUTYLENE IN THE PRESENCE OF BUTADIENE|

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