KR970015550A - Process for preparing tertiary alkyl ethers from olefinic hydrocarbon feedstock - Google Patents

Process for preparing tertiary alkyl ethers from olefinic hydrocarbon feedstock Download PDF

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KR970015550A
KR970015550A KR1019950030859A KR19950030859A KR970015550A KR 970015550 A KR970015550 A KR 970015550A KR 1019950030859 A KR1019950030859 A KR 1019950030859A KR 19950030859 A KR19950030859 A KR 19950030859A KR 970015550 A KR970015550 A KR 970015550A
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hydrogenation
distillation
hydrocarbons
hydrogen
carried out
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KR1019950030859A
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KR100403387B1 (en
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제르벨린 하리
린드크비스트 페트리
자쿨라 주하
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타파니 알호
네스테 오와이
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01Preparation of ethers
    • C07C41/18Preparation of ethers by reactions not forming ether-oxygen bonds
    • C07C41/20Preparation of ethers by reactions not forming ether-oxygen bonds by hydrogenation of carbon-to-carbon double or triple bonds
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/10Process efficiency

Abstract

본 발명은 3차 알킬 에테르의 제조 방법에 관한 것이다.The present invention relates to a process for the preparation of tertiary alkyl ethers.

상기 방법은 촉매의 존재하에, C4내지 C7을 함유하는 포화 또는 단일 불포화 또는 다중 불포화 탄화수소를 함유하는 피드스톡을 다중 불포화 탄화수소에 대해 과량의 수소와 접촉시켜서 다중 불포화 탄화수소의 최소한 일부를 선택적으로 수소화시켜서, 불포화 탄화수소가 주로 단일 불포화 화합물로 이루어진 것이 변형된 탄화수소 피드스톡을 생성시키는 단계; 반응하지 않은 수소의 최소한 일부와 함께 변형된 탄화수소 피드스톡을 적어도 하나의 증류 컬럼을 포함하는 촉매 증류 반응기 시스템에 공급하는 단계; 피드스톡의 C4~7이소올레핀을 촉매의 존재하에 반응시켜서 3차 알킬 에테르를 생성시키는 단계; 반응 혼합물을 증류 컬럼에서 증류시키는 단계; 알킬 에테르, 및 증류의 바닥 생성물을 갖는 모든 비-반응 탄화수소를 회수하는 단계; 주로 포화 C4탄화수소 및 알칼올의 공비혼합물을 함유하는, 증류의 천정 생성물을 배출시키는 단계, 및 컬럼에서 수소를 함유하는 기체상 증류의 양을 조절함에 의해 증류 컬럼의 압력을 실제로 일정하게 유지시키는 단계로 이루어진다.The process selectively contacts at least a portion of the polyunsaturated hydrocarbons by contacting feedstock containing saturated or monounsaturated or polyunsaturated hydrocarbons containing C 4 to C 7 with excess hydrogen to the polyunsaturated hydrocarbons in the presence of a catalyst. Hydrogenation, wherein the unsaturated hydrocarbon consists primarily of monounsaturated compounds to produce a modified hydrocarbon feedstock; Supplying the modified hydrocarbon feedstock with at least a portion of the unreacted hydrogen to a catalytic distillation reactor system comprising at least one distillation column; Reacting C 4-7 isoolefins in the feedstock in the presence of a catalyst to produce tertiary alkyl ethers; Distilling the reaction mixture in a distillation column; Recovering all non-reacted hydrocarbons with alkyl ether, and bottom product of distillation; Evacuating the ceiling product of the distillation, which contains primarily an azeotrope of saturated C 4 hydrocarbons and alkalols, and controlling the amount of gaseous distillation containing hydrogen in the column to actually maintain a constant pressure in the distillation column. Consists of steps.

Description

올레핀성 탄화수소 피드스톡으로부터 3차 알킬 에테르를 제조하기 위한 방법Process for preparing tertiary alkyl ethers from olefinic hydrocarbon feedstock

본 내용은 요부공개 건이므로 전문내용을 수록하지 않았음Since this is an open matter, no full text was included.

제1도는 FCC 가솔린 분할기, 선택성 수소화 장치 및 에테르화 장치로 이루어진, 본 발명에 따르는 TAME 공정의 개략도.1 is a schematic diagram of a TAME process according to the present invention, consisting of an FCC gasoline splitter, a selective hydrogenation unit and an etherification unit.

제2도는 본 발명에서 사용되는 선택성 수소화 장치의 개략도.2 is a schematic diagram of a selective hydrogenation apparatus used in the present invention.

제3도는 3개의 예비 반응기, 생성물 분리 컬럼 및 2개의 측면 반응기로 이루어진 에테르화 장치의 개략도.3 is a schematic representation of an etherification apparatus consisting of three preliminary reactors, a product separation column and two side reactors.

Claims (14)

촉매의 존재하에, C4내지 C7을 함유하는 포화 또는 단일 불포화 또는 다중 불포화 탄화수소를 함유하는 피드스톡을 다중 불포화 탄화수소에 대해 과량의 수소와 접촉시켜서 다중 불포화 탄화수소의 최소한 일부를 선택적으로 수소화시켜서, 불포화 탄화수소가 주로 단일 불포화 화합물로 이루어진 것이 변형된 탄화수소 피드스톡을 생성시키는 단계, 반응하지 않은 수소의 최소한 일부와 함께 변형된 탄화수소 피드스톡을 적어도 하나의 증류 컬럼을 포함하는 촉매 증류 반응기 시스템에 공급하는 단계; 피드스톡의 C4~7이소올레핀을 촉매의 존재하에 반응시켜서 3차 알킬 에테르를 생성시키는 단계; 반응 혼합물을 증류 컬럼에서 증류시키는 단계; 알킬 에테르, 및 증류의 바닥 생성물을 갖는 모든 비-반응 탄화수소를 회수하는 단계; 주로 포화 C4탄화수소 및 알칸올의 공비혼합물을 함유하는, 증류의 천정 생성물을 배출시키는 단계, 및 컬럼에서 수소를 함유하는 기체상 증류의 양을 조절함에 의해 증류 컬럼의 압력을 실제로 일정하게 유지시키는 단계로 이루어지는, 3차 알킬 에테르의 제조 방법.In the presence of a catalyst, at least a portion of the polyunsaturated hydrocarbons are selectively hydrogenated by contacting feedstock containing saturated or monounsaturated or polyunsaturated hydrocarbons containing C 4 to C 7 with excess hydrogen to the polyunsaturated hydrocarbons, Producing unsaturated hydrocarbon feedstocks, wherein the unsaturated hydrocarbons consist primarily of monounsaturated compounds, feeding the modified hydrocarbon feedstocks with at least a portion of the unreacted hydrogen to a catalytic distillation reactor system comprising at least one distillation column step; Reacting C 4-7 isoolefins in the feedstock in the presence of a catalyst to produce tertiary alkyl ethers; Distilling the reaction mixture in a distillation column; Recovering all non-reacted hydrocarbons with alkyl ether, and bottom product of distillation; Evacuating the ceiling product of the distillation, which contains primarily an azeotrope of saturated C 4 hydrocarbons and alkanols, and controlling the amount of gaseous distillation containing hydrogen in the column to actually maintain a constant pressure in the distillation column. A method of preparing a tertiary alkyl ether, consisting of the steps. 제1항에 있어서, 피드스톡의 다중 불포화 탄화수소에 대해 계산하여, 1.001 내지 10-배 과량의 수소가 탄화수소 피드스톡의 수소화를 위해 사용됨을 특징으로 하는 방법.The process of claim 1, wherein 1.001 to 10-fold excess hydrogen is used for hydrogenation of the hydrocarbon feedstock, calculated for the polyunsaturated hydrocarbon of the feedstock. 제1항에 있어서, 수소화 동안 탄화수소 피드스톡 중에 80% 이상의 수소를 용해시킬만큼 충분히 높은 압력에서 수소화가 수행됨을 특징으로 하는 방법.The process of claim 1 wherein the hydrogenation is carried out at a pressure high enough to dissolve at least 80% hydrogen in the hydrocarbon feedstock during the hydrogenation. 제3항에 있어서, 15 내지 115 바아의 압력에서 수소화가 수행됨을 특징으로 하는 방법.4. The process of claim 3, wherein hydrogenation is carried out at a pressure of 15 to 115 bar. 제3항에 있어서, 증류 동안 기체상 중에 수소를 유지시키기 위해 수소화 보다 낮은 압력에서 증류수가 수행됨을 특징으로 하는 방법.4. The process of claim 3, wherein distilled water is carried out at a lower pressure than hydrogenation to maintain hydrogen in the gas phase during distillation. 제1항에 있어서, 지지된 귀금속 촉매 및 지지된 니켈 촉매로 구성된 군으로부터 선택된 촉매의 존재하에 수소화가 수행됨을 특징으로 하는 방법.The process according to claim 1, wherein the hydrogenation is carried out in the presence of a catalyst selected from the group consisting of supported noble metal catalysts and supported nickel catalysts. 제6항에 있어서, 알루미나 상의 팔라듐으로 이루어진 촉매의 존재하에 수소화가 수행되며, 촉매의 전체 중량에 대해 계산하여 팔라듐의 농도가 0.2 내지 5중량%임을 특징으로 하는 방법.The process according to claim 6, wherein hydrogenation is carried out in the presence of a catalyst consisting of palladium on alumina, wherein the concentration of palladium is from 0.2 to 5% by weight, calculated on the total weight of the catalyst. 제1항에 있어서, 촉매 오염을 보상하기 위해 조작 동안 수소화의 온도가 40℃로부터 130℃까지 증가함을 특징으로 하는 방법.The method of claim 1, wherein the temperature of hydrogenation increases from 40 ° C. to 130 ° C. during the operation to compensate for catalyst contamination. 제1항에 있어서, 수소화가 2개의 연속 반응기에서 수행됨을 특징으로 하는 방법.The method of claim 1 wherein the hydrogenation is carried out in two continuous reactors. 제1항에 있어서, 수소화가 순수 수소 기체의 사용에 의해 수행됨을 특징으로 하는 방법.The process according to claim 1, wherein the hydrogenation is carried out by the use of pure hydrogen gas. 제1항에 있어서, 수소화가 10 내지 70중량% 휘발성 저분자량 파라핀을 함유하는 수소 기체의 사용에 의해 수행됨을 특징으로 하는 방법.The process according to claim 1, wherein the hydrogenation is carried out by the use of hydrogen gas containing 10 to 70% by weight volatile low molecular weight paraffins. 제1항에 있어서, 5몰% 과량의 수소를 수소화 공정에 공급하고, 수소화 공정의 압력을 15 바아 이상으로 유지시키고, 증류의 압력을 10 바아 이하로 유지시킴을 특징으로 하는 방법.The process according to claim 1, wherein 5 mole% excess hydrogen is supplied to the hydrogenation process, the pressure of the hydrogenation process is maintained at 15 bar or more, and the pressure of distillation is maintained at 10 bar or less. 제1항에 있어서, 알칸올이 메탄올 또는 에탄올로 이루어짐을 특징으로 하는 방법.The method of claim 1 wherein the alkanol consists of methanol or ethanol. 제1항에 있어서, 증류로부터 배출되는 증류물의 양이 공급물 중에 존재하는 C4탄화수소의 양에 상응함을 특징으로 하는 방법.The process of claim 1 wherein the amount of distillate exiting the distillation corresponds to the amount of C 4 hydrocarbons present in the feed. ※ 참고사항 : 최초출원 내용에 의하여 공개하는 것임.※ Note: The disclosure is based on the initial application.
KR1019950030859A 1995-09-20 1995-09-20 Process for preparing tertiary alkyl ethers from olefinic hydrocarbon feedstock KR100403387B1 (en)

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