CN1044805C - Etherification reaction technology and equipment for light hydrocarbon and aliphatic alcohol - Google Patents
Etherification reaction technology and equipment for light hydrocarbon and aliphatic alcohol Download PDFInfo
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- CN1044805C CN1044805C CN94110775A CN94110775A CN1044805C CN 1044805 C CN1044805 C CN 1044805C CN 94110775 A CN94110775 A CN 94110775A CN 94110775 A CN94110775 A CN 94110775A CN 1044805 C CN1044805 C CN 1044805C
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- Y—GENERAL 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
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Abstract
The present invention relates to a preparation process for producing ether by reaction distillation and equipment thereof. The catalytic distillation equipment adopted by the present invention can simultaneously implement the processes of selective hydrogenation to remove di-olefin, the etherification reaction of tertiary olefin and fatty alcohol and product separation, and a reaction distillation tower is divided into three sections including an upper portion, a middle portion and a lower portion, wherein the middle reaction section contains two mixed phase reaction zones and one catalytic distillation zone, and the interior of each reaction zone simultaneously is provided with two middle fraction zones. A catalyst is bulk and is easy to load and unload.
Description
The present invention relates to a kind of new preparation method of alkyl oxide, a kind of catalytic distillation method and the equipment that especially in the etherification reaction that contains tertiary olefin class and Fatty Alcohol(C12-C14 and C12-C18), use.
People are known to cover unsticking soil, silicotungstic acid, under the effect of storng-acid cation exchange resin or molecular sieve catalyst, produce alkyl oxide by hydrocarbon polymer that contains tertiary olefin and Fatty Alcohol(C12-C14 and C12-C18) reaction, traditional mode adopts fixed-bed reactor, under liquid phase state, react, in order to take out reaction heat, more adopt the inner array tubular reactors or respond that (USP 4 for material outer circulation refrigerative cartridge reactor, 198,530) and expanded bed reactor (Fr 2455019, Fr 2440931) because reaction is subjected to the restriction of equilibrium conversion, in order to improve transformation efficiency, adopt reaction one to separate and react separation processes again and again again and again, long flow path, facility investment is big, the energy consumption height, succeeding in developing of catalytic distillation technology makes reaction and is separated in same equipment and carry out simultaneously, simplified technical process.Because resultant constantly shifts out reaction zone, destroyed the balance of reaction, (USP 4 also to have improved transformation efficiency, 439350), but catalyst loading structure more complicated in the tower, in order to guarantee the transformation efficiency of reactant, the height of catalytic distillation tower is invested also bigger also than higher.
The objective of the invention is to simplify the catalyst loading structure of reactive distillation column, reduce production costs, reduce energy consumption, reduce the tower height degree, reduce investment, improve the transformation efficiency of reactant.
For achieving the above object, design of the present invention is to adopt novel catalytic distillation method and equipment:
The feature of reactive distillation column of the present invention is to have comprised two mixed phase catalysis reaction districts and a reactive distillation zone in the conversion zone; Be provided with two middle fractionation zones in reaction zone, reactant is selected diolefin in the hydrogenation and removing raw material at first catalytic reaction zone, and carries out the etherification reaction of tertiary olefin and Fatty Alcohol(C12-C14 and C12-C18); After in middle fractionation zone, removing the ether that in first etherification reaction zone, generates, enter in second catalytic reaction zone and proceed etherification reaction; After removing the ether of second catalytic reaction zone generation, material enters reactive distillation zone, carries out simultaneously at this etherification reaction and product separation, meets the requirements of transformation efficiency.
Now in conjunction with the accompanying drawings reactive distillation technology of the present invention is elaborated: we do as a whole narration the (also can make a tower) with tower A and B.Reactive distillation column is divided into three parts: top is conventional rectifying section (26), the bottom is conventional stripping stage (7), the feature of middle part conversion zone comprises: catalytic reaction zone I a (4), middle fractionation zone I b (3), catalytic reaction zone II a (15), the catalytic distillation zone II c on middle fractionation zone II b (21) and its top, catalytic reaction zone I a, be respectively equipped with beds (4a) among the II a, (4b), (4c) with (15), and at least 1 liquid channel (5), (16), article at least 1, vapor phase channel (6), (17), be equipped with among the bed I a and select hydrogenation catalyst and catalyst for etherification, also can be that the catalyst for etherification of selecting hydrogenating function is arranged, in II a (15) bed catalyst for etherification is housed, middle fractionation zone I b, respectively the plate or the filler of at least one routine among the II b; Be provided with at least two beds (22), (23) among the catalytic distillation zone II c, and establish at least one plate (25) and at least one vapor phase channel (24) between bed.
The hydrocarbon polymer that contains tertiary olefin mixes by a certain percentage with hydrogen, methyl alcohol, through pipeline (1), preheater (2), enter reaction zone I a top, and pass beds (4a), (4b), (4c), at first select diolefin, alkynes in the hydrogenation and removing raw material; Right Hou is carried out etherification reaction, emits reaction heat, and when temperature was elevated to the bubble point of reaction mass under the working pressure, partial reaction material vaporization absorption reaction heat made temperature-stable; Reaction back mixture flow is to stripping stage (7); After (7) vapor-phase material that rises and vapor-phase material mixing of reacting generation, disengaging zone I b (3) in vapor phase channel (6) enters; Liquid phase material after the separation flows to the top of stripping stage (7) through liquid channel (5), vapor-phase material after the separation is through pipeline (12), enter interchanger (13), after heat exchange liquefaction, enter catalytic reaction zone II a (15) by pipeline (14), carry out etherification reaction, partial reaction material vaporization absorption reaction heat, the post reaction mixture materials flow is to the B tower bottom; Vapor-phase material is disengaging zone II b (21) in vapor phase channel (17) flows to; Liquid phase material after the separation flows to the B tower bottom through liquid channel (16); Flow out through pipeline (17a), a part is the heat exchange vaporization in interchanger (13), the bottom of disengaging zone II b in pipeline (18) enters; Another part enters the top of I b in disengaging zone in the A tower through pipeline (19) and (20), the vapor-phase material after separating from II b is through vapor phase channel (24) beds of having mercy on, and passes and carry out the caloic exchange on column plate (25), and vapor-phase material enters rectifying section (26); Liquid phase material under separating flows downward, and passes the beds (23) of II c, carries out etherification reaction; Liquid phase material is gone up with vapor-phase material at separation tray (25) and is carried out the caloic transmission, and the liquid phase material after stripping stage (7) separates flows to the A tower bottom and flows out through pipeline (8), and a part is vaporized at reboiler (9), at the bottom of pipeline (10) returns the A tower; Another part goes out device through pipeline (11), i.e. the ether compound product.Vapor-phase material after rectifying section (26) separates after pipeline (27) enters condenser (28) condensation, enters return tank (29).One one is back to the B top of tower through pipeline (30); Another part enters downstream unit through pipeline (31).
Effect of the present invention has reached the purpose of invention, because the progress of equipment and technology adopts repeatedly Reaction Separation to destroy the balance of reaction, transformation efficiency is improved; Catalyzer in bulk makes filling structure simple, reduces running cost, and the tower total height decreases than existing catalysis-distillation equipment.The investment of catalysis-distillation equipment is saved.
By means of embodiment effect of the present invention is described below;
Embodiment 1.
Iso-butylene and methyl alcohol reaction that the present invention is used for mixed c 4 generate methyl tertiary butyl ether.Iso-butylene in the material carbon four is 36.5% (M/M), butadiene content is that 1.0% (M/M) is according to technology of the present invention, be respectively 0.7mPa (A tower) and 0.6mPa (B tower) at pressure, reflux ratio 1.0, alfin ratio 1.05 (mol/mol), temperature is 25-140 ℃, and conversion for isobutene is 99%, the content≤20PPM of divinyl.The purity of methyl tertiary butyl ether is 98%.
Embodiment 2.
The tertiary olefin (2-methyl butene-1 and 2-methyl butene-2) that the present invention is used for the catalyzed carbon 5 distillate generates tert amyl methyl ether(TAME) with the methyl alcohol reaction.2-methyl butene-1 is 7.5% in the material carbon 5 distillate, 2-methyl butene-2 is 15.52%, diolefin (isoprene, cyclopentadiene, along pentadiene) be 1.2%: according to technology of the present invention, at pressure is 0.4MPa (A tower) and 0.3MPa (B tower), alfin ratio is 1.05 (MOL/MOL), reflux ratio 1.0, temperature is 25-140 ℃, and 2-methyl butene-1 has 99% to be converted into tert amyl methyl ether(TAME), and 2-methyl butene-2 has 95% to be converted into tert amyl methyl ether(TAME), the content of diolefin is reduced to below the 100PPH, and the purity of tert amyl methyl ether(TAME) is 98%.
Embodiment 3.
The present invention is used for tertiary olefin (the 2-methyl butene-1 of catalyzed carbon 5 distillate and carbon six fractions, 2-methyl butene-2,2,3-neohexene-1,2-methylpentene-1,2-methylpentene-2, suitable-3-methylpentene-2 and anti--3-methylpentene-2) produce methyl alcohol tert-amyl ether and methyl alcohol uncle hexyl ether with the methyl alcohol reaction, 2-methyl butene-1 is 3.80% in the raw material, 2-methyl butene-2 is 7.76%, 2,3-neohexene-1 is 0.26%, and 2-methylpentene-1 is 1.55%, 2-methylpentene-2 is 2.46%, suitable-3-methylpentene-2 is 2.38%, anti--3-methylpentene-2 is 2.18%, diolefin content is 1.52%; According to technology of the present invention, be respectively 0.2NPa (A tower) and 1.0mPa (B tower) at pressure, reflux ratio 1.0, alfin ratio is 1.05 (moP/moP), temperature is 25-140 ℃, 2-methyl butene-1 has 99.% to be converted into tert amyl methyl ether(TAME), and 2-methyl butene-2 has 94% to be converted into tert amyl methyl ether(TAME); 2-methylpentene-1,2-methylpentene-2, anti--3-methylpentene-2 and suitable-3-methylpentene-2 have 99% respectively, 77%, 65% and 38% is converted into the methyl-tert hexyl ether, and diolefin content is reduced to 150PPM, and 60% tert amyl methyl ether(TAME) and 38% methyl-tert hexyl ether are arranged in the product.
Claims (5)
1. the preparation method of an alkyl oxide, by the lighter hydrocarbons that contain tertiary olefin and Fatty Alcohol(C12-C14 and C12-C18) through mix, preheating, under catalyst action, carry out etherification reaction, this etherification reaction and product separation carry out in catalytic distillation tower simultaneously, it is characterized in that:
A. in catalytic reaction zone I a, under catalyst action, select hydrogenation and removing diolefin and etherification reaction through the reaction raw materials of preheating, flow to stripping stage under directly;
B. the product and the unreacted raw material that in middle fractionation zone I b, separate etherificate through the vapor-phase material at vapor phase channel upper reaches;
C. the unreacted material of separating through I b enters catalytic reaction zone II a through interchanger (13) and liquid phase material heat exchange from (17) after the liquefaction, proceeds etherification reaction;
D. fractionation zone II b product separation and unreacted material during reaction mass flows on the vapor phase channel (17) of II a;
E. the unreacted material behind II b enters catalytic distillation zone II c in the upper reaches again through vapor phase channel (24), carries out the caloic transmission on the tower tray of catalyst bed interlayer;
F. the unreacted vapor-phase material from II c flows out from cat head after distilling period (26) separates, and a part refluxes after condensation, and a part goes out device;
G. the liquid phase material from rectifying section (26) directly enters reactive distillation zone II c, on the tower tray of catalyst bed interlayer, carry out the caloic transmission, and flow downward and pass beds and carry out etherification reaction simultaneously, liquid phase material through reactive distillation zone II c separates in middle fractionation zone II b, liquid phase material after the separation is through (17) pipeline, a part is advanced vaporization in the interchanger (13), the bottom of fractionation zone II b in pipeline (18) enters, another part is the top of fractionation zone I b in pipe (19) and (20) enters, and the liquid phase material of separating through I b enters the top of stripping stage through the liquid channel of I a;
H. flow out through pipeline (8) through the isolating liquid phase material of stripping stage, a part is at the bottom of turning back to tower after reboiler (9) vaporization, and another part goes out device through (11) pipe, is product ether;
I. when granules of catalyst bigger, or porosity also can not establish vapor phase channel and liquid channel in the reaction bed when big, vapor-phase material can convection current pass bed.
2. by the described method of claim 1, it is characterized in that: described light hydrocarbon etherifying reaction, be meant that lighter hydrocarbons and alcohols generate the reaction of ether under catalyst action, lighter hydrocarbons are meant the alkene of C3～C7, and alcohols is meant Fatty Alcohol(C12-C14 and C12-C18) such as methyl alcohol, propyl alcohol, butanols, generates corresponding ether compound thus, above-mentioned lighter hydrocarbons can be same carbon number hydro carbons, also can be two or more hydrocarbon mixture, the ethers of generation can be the ether with carbon number, also can be the ether of different carbon numbers.
3. by the described method of claim 1, it is characterized in that: the temperature control of light hydrocarbon etherifying reaction is to be foundation to satisfy the etherification reaction requirement, reaction system difference, temperature of reaction is also different, and generally between 25～200 ℃, working pressure is that reactant ties up to the saturated vapor pressure under the temperature of reaction.
4. by the described method of claim 1, it is characterized in that the reaction of described lighter hydrocarbons ether, if raw material is the hydrocarbon of single carbon number, used alcohol is methyl alcohol, can obtain purity like this at the bottom of the tower greater than 98% methyl-tert alkyl oxide, cat head will obtain reacting residual hydrocarbon and a small amount of azeotropic is formed methyl alcohol, if raw material is the hydrocarbon of two kinds of carbon numbers, used alcohol is methyl alcohol, can obtain corresponding two kinds of methyl-tert alkyl oxides and remaining wherein than the mixture of heavy hydrocarbon like this at the bottom of the tower, cat head obtains reacting the methyl alcohol of residue than lighter hydrocarbons and a small amount of azeotropic composition.
5. produce the equipment of alkyl oxide by lighter hydrocarbons and Fatty Alcohol(C12-C14 and C12-C18) for one kind, adopt catalytic distillation tower to carry out catalyzed reaction and separate, tower divides three sections of upper, middle and lowers, and top is rectifying section, and the bottom is a stripping stage, and the middle part is a conversion zone, it is characterized in that:
A. Zhong Bu conversion zone comprises catalytic reaction zone I a, and the middle fractionation zone I b on top, and top/or at the catalytic reaction zone II a of another tower bottom and up middle fractionation zone II b successively, catalytic distillation zone II c;
B. I a comprises two above catalytic bed (4a), (4b), (4c);
C. I a be provided with/or do not establish at least 1 gas phase channel (6) and at least 1 liquid channel (5);
D. when vapour, liquid channel, a closure plate of shutting is arranged at the top of beds (4) and (15);
E. II b is an at least one plate;
F. II c is at least two beds, and at least one plate between bed is provided with at least one vapor phase channel in the beds.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94110775A CN1044805C (en) | 1994-08-30 | 1994-08-30 | Etherification reaction technology and equipment for light hydrocarbon and aliphatic alcohol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94110775A CN1044805C (en) | 1994-08-30 | 1994-08-30 | Etherification reaction technology and equipment for light hydrocarbon and aliphatic alcohol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1117959A CN1117959A (en) | 1996-03-06 |
| CN1044805C true CN1044805C (en) | 1999-08-25 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94110775A Expired - Fee Related CN1044805C (en) | 1994-08-30 | 1994-08-30 | Etherification reaction technology and equipment for light hydrocarbon and aliphatic alcohol |
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| Country | Link |
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| CN (1) | CN1044805C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1085648C (en) * | 1997-05-07 | 2002-05-29 | 中国石化齐鲁石油化工公司 | Light hydrocarbon etherifying technology |
| CN109651057A (en) * | 2017-10-10 | 2019-04-19 | 中国石油化工股份有限公司 | The method for preparing iso-amylene |
| CN109651063A (en) * | 2017-10-10 | 2019-04-19 | 中国石油化工股份有限公司 | The preparation method of iso-amylene |
| CN109173310A (en) * | 2018-08-29 | 2019-01-11 | 张家港市科华化工装备制造有限公司 | Dimethoxym ethane rectifying column |
| CN114011341A (en) * | 2021-11-15 | 2022-02-08 | 丹东明珠特种树脂有限公司 | Catalytic distillation tower and high-purity MTBE preparation system for deeply removing isobutene |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55323A (en) * | 1978-06-17 | 1980-01-05 | Fuji Sekiyu Kk | Preparation of methyl tertiary-butyl ether |
| US4418219A (en) * | 1981-03-02 | 1983-11-29 | National Distillers And Chemical Corporation | Preparation of methyl tertiary-butyl ether |
-
1994
- 1994-08-30 CN CN94110775A patent/CN1044805C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55323A (en) * | 1978-06-17 | 1980-01-05 | Fuji Sekiyu Kk | Preparation of methyl tertiary-butyl ether |
| US4418219A (en) * | 1981-03-02 | 1983-11-29 | National Distillers And Chemical Corporation | Preparation of methyl tertiary-butyl ether |
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| Publication number | Publication date |
|---|---|
| CN1117959A (en) | 1996-03-06 |
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Address after: No. 6 Huixin East Street Jia, Chaoyang District, Beijing: 100029 Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: Sinopec qilu petrochemical company Address before: No. 6 Huixin East Street Jia, Chaoyang District, Beijing: 100029 Patentee before: China Petrochemical Corporation Patentee before: Sinopec qilu petrochemical company |
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Effective date of registration: 20071228 Address after: Zibo City, Shandong Province, Linzi District, China Petrochemical Qilu Branch, Ministry of Science and Technology zip code: 100029 Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Address before: No. 6 Huixin East Street Jia, Chaoyang District, Beijing: 100029 Patentee before: CHINA PETROLEUM & CHEMICAL Corp. Patentee before: Sinopec qilu petrochemical company |
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