CN102442976B - Olefin Epoxidation Method - Google Patents
Olefin Epoxidation Method Download PDFInfo
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- CN102442976B CN102442976B CN201010511515.XA CN201010511515A CN102442976B CN 102442976 B CN102442976 B CN 102442976B CN 201010511515 A CN201010511515 A CN 201010511515A CN 102442976 B CN102442976 B CN 102442976B
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- 238000000034 method Methods 0.000 title claims abstract description 70
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 40
- 238000006735 epoxidation reaction Methods 0.000 title claims abstract description 35
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 13
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 160
- 238000006243 chemical reaction Methods 0.000 claims abstract description 80
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000000203 mixture Substances 0.000 claims abstract description 35
- 239000002002 slurry Substances 0.000 claims abstract description 29
- 239000011949 solid catalyst Substances 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 239000011541 reaction mixture Substances 0.000 claims description 19
- 230000009466 transformation Effects 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 abstract description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 30
- 239000003550 marker Substances 0.000 description 21
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 15
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 15
- 150000002924 oxiranes Chemical class 0.000 description 13
- 238000004364 calculation method Methods 0.000 description 11
- 238000001514 detection method Methods 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000007086 side reaction Methods 0.000 description 5
- 239000013543 active substance Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 2
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 238000003746 solid phase reaction Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- UEKQGZQLUMSLNW-UHFFFAOYSA-N Propyl isome Chemical compound C1=C2C(C(=O)OCCC)C(C(=O)OCCC)C(C)CC2=CC2=C1OCO2 UEKQGZQLUMSLNW-UHFFFAOYSA-N 0.000 description 1
- NWGKJDSIEKMTRX-MDZDMXLPSA-N Sorbitan oleate Chemical compound CCCCCCCC\C=C\CCCCCCCC(=O)OCC(O)C1OCC(O)C1O NWGKJDSIEKMTRX-MDZDMXLPSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 1
- 229920000053 polysorbate 80 Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
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- Epoxy Compounds (AREA)
Abstract
本发明提供了一种烯烃环氧化方法，包括以下步骤：(1)在烯烃环氧化反应的条件下，在第一固体催化剂的存在下，使含有溶剂、烯烃和过氧化氢的第一混合物料在移动床反应器中进行环氧化反应，反应的程度使过氧化氢的转化率达到50％以上；(2)在烯烃环氧化反应的条件下，将步骤(1)得到的反应混合物和第二固体催化剂引入到淤浆床反应器中进行环氧化反应，反应的程度使过氧化氢的总转化率达到95％以上。本发明提供的方法使用了移动床反应器和淤浆床反应器的组合，克服了只使用移动床反应器进行反应时存在的过氧化氢的转化率低的缺点，同时也克服了只使用淤浆床反应器进行反应时存在的环氧丙烷的选择性低的缺点。The present invention provides a kind of olefin epoxidation method, comprises the following steps: (1) under the condition of olefin epoxidation reaction, in the presence of the first solid catalyst, make the first olefin containing solvent, olefin and hydrogen peroxide The mixed material is carried out epoxidation reaction in the moving bed reactor, and the degree of reaction makes the conversion rate of hydrogen peroxide reach more than 50%; (2) under the condition of olefin epoxidation reaction, the reaction obtained in step (1) is The mixture and the second solid catalyst are introduced into the slurry bed reactor to carry out the epoxidation reaction, and the degree of reaction makes the total conversion rate of hydrogen peroxide reach more than 95%. The method provided by the invention has used the combination of moving bed reactor and slurry bed reactor, has overcome the shortcoming that the conversion rate of hydrogen peroxide that exists when only using moving bed reactor is reacted is low, has also overcome simultaneously only using slurry The low selectivity of propylene oxide exists when the slurry bed reactor reacts.
Description
Technical field
The present invention relates to a kind of olefin epoxidation process.
Background technology
At present, mainly adopt in the world chlorohydrination and conjugated oxidation to produce propylene oxide.Chlorohydrination, because there is pollution problem, will progressively be eliminated; And conjugated oxidation is subject to the restriction of by product outlet application, also can not be developed on a large scale.Therefore, the production method of the propylene oxide of prior art is all seriously restricting the production of propylene oxide.Occurred in recent years a kind of preparation method with new propylene oxide, the method, under the catalysis of HTS, is utilized oxidants hydrogen peroxide by epoxidation of propylene and synthesizing epoxypropane.The method has the advantages such as mild condition, process environment be friendly and pollution-free, forms as producing the novel environment-friendly process of propylene oxide.
For example, CN1671678A adopts double-fixed bed reactor process to carry out epoxidation reaction, and first reactor is isothermal fixed-bed reactor, and second reactor is insulation fix bed reactor.But the shortcoming that the method exists is that the conversion of the hydrogen peroxide of use in reaction is incomplete, unreacted completely hydrogen peroxide can decompose and produce oxygen in knockout tower, to device, brings potential safety hazard, even can cause exploding when serious.
CN1449392A discloses a kind of method of using superoxide to manufacture epoxy alkane, the method is in the reactor that a part of catalyzer is respectively housed of at least two arranged in series, under the existence of catalysts and solvents, by the reaction of alkene and superoxide, manufacture the method for epoxy alkane, according to the method, only in the first reactor, add superoxide, one or several reactor below does not add fresh superoxide, and just use from the superoxide not consuming in reactor above, thereby the hydrogen peroxide in reaction is transformed completely.The reactor using in the method is fixed-bed reactor or fluidized-bed reactor, and uses at least two reactors, preferably uses 3 reactors of series connection.The shortcoming that the method exists is when using two minimum reactors, the conversion of hydrogen peroxide is still incomplete, when using plural tandem reactor, cause increasing substantially of equipment cost, and the reaction time of the reactor of a plurality of series connection is long, in reaction process, uncontrollable factor is too much.
Therefore, in the urgent need to developing a kind of hydrogen peroxide using in reaction that can make, transform completely and the high olefin epoxidation process of selectivity of propylene oxide.
Summary of the invention
The conversion that the object of the invention is to overcome the hydrogen peroxide using in the reaction existing in prior art not exclusively and the low shortcoming of selectivity of propylene oxide, provides a kind of hydrogen peroxide using in reaction that can make to transform completely and the high olefin epoxidation process of selectivity of the propylene oxide obtaining.
In order to realize goal of the invention of the present invention, the invention provides a kind of olefin epoxidation process, wherein, the method comprises the following steps:
(1) under the condition of epoxidation reaction of olefines, under the existence of the first solid catalyst, make the first mixture that contains solvent, alkene and hydrogen peroxide in moving-burden bed reactor, carry out epoxidation reaction, the degree of reaction reaches more than 50% the transformation efficiency of hydrogen peroxide;
(2) under the condition of epoxidation reaction of olefines, the reaction mixture that step (1) is obtained and the second solid catalyst are incorporated in slurry bed reactor and carry out epoxidation reaction, and the degree of reaction reaches more than 95% the transformation efficiency of total hydrogen peroxide.
Method provided by the invention is by being used the combination of moving-burden bed reactor and slurry bed reactor, overcome the shortcoming of the low conversion rate of the hydrogen peroxide existing while only using moving-burden bed reactor to react, also overcome the low shortcoming of selectivity of the propylene oxide existing while only using slurry bed reactor to react simultaneously, without using the too much reactor of series connection, reduced equipment cost and also shortened the production cycle simultaneously.
Embodiment
The invention provides a kind of olefin epoxidation process, wherein, the method comprises the following steps:
(1) under the condition of epoxidation reaction of olefines, under the existence of the first solid catalyst, make the first mixture that contains solvent, alkene and hydrogen peroxide in moving-burden bed reactor, carry out epoxidation reaction, the degree of reaction reaches more than 50% the transformation efficiency of hydrogen peroxide;
(2) under the condition of epoxidation reaction of olefines, the reaction mixture that step (1) is obtained and the second solid catalyst are incorporated in slurry bed reactor and carry out epoxidation reaction, and the degree of reaction reaches more than 95% the total conversion rate of hydrogen peroxide.
The present invention is by using the combination of moving-burden bed reactor and slurry bed reactor, can make the hydrogen peroxide using in reaction transform completely, and the probability that side reaction occurs is very low, the selectivity that can keep higher propylene oxide, without using the too much reactor of series connection, reduced equipment cost and also shortened the production cycle simultaneously.
According to the present invention, the optionally method of calculation of the transformation efficiency of hydrogen peroxide in step (1) and the total conversion rate of hydrogen peroxide, propylene oxide are as follows:
(I)
Mole number * 100% of the hydrogen peroxide of charging in the mole number/step (1) of the hydrogen peroxide being converted in the transformation efficiency=step (1) of the hydrogen peroxide in step (1)
(II)
Total mole number * 100% of the hydrogen peroxide of the total mole number/charging of the hydrogen peroxide of the total conversion rate of hydrogen peroxide=be converted
(III)
Total mole number sum * 100% of the epoxide of the mole number/generation of the propylene oxide of the selectivity=generation of propylene oxide.
Wherein, the detection method of the total mole number of the epoxide of the mole number of hydrogen peroxide, the mole number of propylene oxide and generation is conventionally known to one of skill in the art, for example, the mole number of hydrogen peroxide can adopt iodimetry,iodometry to detect, and the total mole number of the mole number of propylene oxide and the epoxide of generation can adopt chromatogram marker method to detect.
According to the present invention, described moving-burden bed reactor is a kind of in order to realize the reactor of the continuous feeding and discharging of gas-solid phase reaction process or liquid and solid phase reaction process.Therefore in moving-burden bed reactor, because the back-mixing of material is very little, while using moving-burden bed reactor to react, be difficult for side reaction occurs, can guarantee the selectivity of propylene oxide, but that the problem existing is the transformation efficiency of hydrogen peroxide is relatively low.
According to the present invention, in described the first mixture, the content of solvent, alkene and hydrogen peroxide can in very large range change, and under preferable case, the mol ratio of described solvent, alkene and hydrogen peroxide is 4-15: 0.5-5: 1.
Under preferable case, described the first mixture also contains tensio-active agent, the gross weight of described the first mixture of take is benchmark, the content of described tensio-active agent is 0.1-1 % by weight, described tensio-active agent can be oil soluble surfactant and/or water soluble surfactant active, for example, can be sorbester p17 and/or tween 80.
In reaction system, add tensio-active agent, at water, formed emulsion, the solubleness of propylene in system increases, and the effective rate of utilization of propylene increases, thereby speed of response is accelerated, meanwhile, the propylene oxide of generation and the intermiscibility of emulsion increase, and have accelerated the velocity of diffusion of propylene oxide at catalyst surface, shortened the residence time at catalyst surface, the carrying out of having slowed down side reaction, reaction preference improves, and catalyst life is elongated.
In the present invention, to the kind of described solvent, be conventionally known to one of skill in the art, for example, described solvent is that water, acetonitrile and carbonatoms are at least one in the alcohol of 1-6, described carbonatoms is that the alcohol of 1-6 can be methyl alcohol, ethanol, propyl alcohol and isomer thereof, butanols and isomer thereof, amylalcohol and isomer thereof, particular methanol.
According to the present invention, the reaction of described moving-burden bed reactor can in very large range change, under preferable case, the reaction conditions of the moving-burden bed reactor of telling can comprise: temperature can be 30-90 ℃, is preferably 40-80 ℃, pressure can be 0.5-4.5MPa, be preferably 0.6-3MPa, the reaction times can be 0.2-10 hour, is preferably 1-5 hour, pH can be 5-8, is preferably 5.5-7.
Slurry bed reactor used in the present invention claims again paste state bed reactor, refers to that the small solid particulate of catalyzer is suspended in the reactor in liquid medium.The material back-mixing of paste state bed reactor is large, and after reaction finishes, general catalyzer and material carry out separatedly just carrying out the reaction of lower batch afterwards.In described slurry-bed reaction, because catalyzer and reaction mass mix, therefore, the transformation efficiency of hydrogen peroxide is higher, but due to the cause of back-mixing, is easy to occur side reaction, thereby causes the selectivity of propylene oxide lower.
According to the present invention, the reaction conditions of described slurry bed reactor can in very large range change, under preferable case, the reaction conditions of described slurry bed reactor can comprise: temperature is 30-90 ℃, be preferably 40-80 ℃, pressure is 0.5-4.5MPa, is preferably 0.6-3MPa, time is 0.2-10 hour, is preferably 0.4-4h
-1, the reaction mixture obtaining with respect to the step (1) of 100 weight parts, the consumption of described the second solid catalyst is 3-10 weight part, is preferably 4-9 weight part.
In the present invention, in moving-burden bed reactor, in the first solid catalyst used and slurry bed reactor, the kind of the second solid catalyst used has no particular limits, they can be identical or different, under preferable case, described the first solid catalyst and the second solid catalyst can be titanium-silicon molecular sieve catalyst, when using in moving-burden bed reactor, described titanium-silicon molecular sieve catalyst can be powder.
In a preferred embodiment of the present invention, method of the present invention also comprises: carry out epoxidation reaction in entering slurry-phase reactor before, the reaction mixture obtaining in step (1) is carried out to separation, obtain containing alkene and propylene oxide and do not contain the first logistics of hydrogen peroxide and the second logistics that contains unreacted hydrogen peroxide, solvent and water; And in the second logistics, introduce alkene and obtain the second mixture, afterwards the second mixture is incorporated in slurry bed reactor and is reacted.The reaction mixture obtaining in step (1) is carried out to separation can avoid the ring texture of the propylene oxide that obtains in moving-burden bed reactor to rupture in slurry bed reactor, thereby reduced the generation of by product, can further improve the selectivity of propylene oxide.The amount of the alkene of described introducing can in very large range change, and under preferable case, with respect to the unreacted hydrogen peroxide of 100 weight parts, the amount of the alkene of introducing in the second logistics is 100-200 weight part.
In another preferred embodiment of the present invention, method of the present invention can also comprise: carry out epoxidation reaction in the reaction mixture that step (1) is obtained is incorporated into slurry bed reactor before, in the reaction mixture obtaining in described step (1), fill into alkene, the described amount that fills into alkene can in very large range change, under preferable case, the described amount that fills into alkene makes in described reaction mixture, with respect to the unreacted hydrogen peroxide of 100 weight parts, the content of alkene is 100-200 weight part.
In the present invention, the kind of described alkene is conventionally known to one of skill in the art, for example, described alkene is that carbonatoms is the alkene of 2-8, comprise one or more in ethene, propylene and isomer thereof, butylene and isomer thereof, amylene and isomer thereof, hexene and isomer thereof, heptene and isomer thereof and octene and isomer thereof, preferably propylene.
Below by specific embodiment, the present invention is described in more details.
Embodiment 1
(1) HTS fine catalyst is loaded in moving-burden bed reactor (purchased from new capital, Chengdu Yong Tong machine works), the concentration of catalyzer in material is 5 % by weight.The first mixture that contains propylene, methyl alcohol and hydrogen peroxide is incorporated in moving-burden bed reactor, and wherein, in described the first mixture, the mol ratio of methyl alcohol, propylene and hydrogen peroxide is 10: 4: 1.The condition of described reaction comprises: temperature is 35 ℃, pressure is 1MPa, time is 8 hours, with ammoniacal liquor, regulate the pH=5 of the first mixture material, by the amount of hydrogen peroxide in mixture after iodimetry,iodometry method detection reaction, and according to the calculation formula (I) shown in above, calculate the transformation efficiency of hydrogen peroxide, result is as shown in table 1.By the amount of the propylene oxide of generation in chromatogram marker method detecting step (1), and by the amount of total epoxide of generation in chromatogram marker method detecting step (1).
(2) reaction mixture step of 100 weight parts (1) being obtained and the HTS powder of 5 weight parts (Hunan Jian Chang company limited, HTS) be incorporated in slurry bed reactor (purchased from Tianjin Ao Zhan Science and Technology Ltd.) and carry out epoxidation reaction, the temperature of reaction is 85 ℃, pressure is 4MPa, time is 1 hour, by the amount of hydrogen peroxide in mixture after iodimetry,iodometry detection reaction, and by the amount of the propylene oxide of generation in chromatogram marker method detecting step (2), and by the amount of the middle total epoxide generating of chromatogram marker method detecting step (1).And respectively according to the calculation formula (II) shown in above and (III), the calculating total conversion rate of hydrogen peroxide and the selectivity of propylene oxide, result is as shown in table 1.
Comparative example 1
According to the method identical with embodiment 1, prepare propylene oxide, difference is that the reactor using in step (2) is the moving-burden bed reactor with identical in step (1).The condition of described reaction comprises: temperature is 35 ℃, and pressure is 1MPa, and liquid volume air speed is 0.5h
-1with ammoniacal liquor, regulate the pH=5 of the first mixture material, by the amount of hydrogen peroxide in mixture after iodimetry,iodometry detection reaction, and by the amount of the propylene oxide of generation in chromatogram marker method detecting step (2), and by the amount of the middle total epoxide generating of chromatogram marker method detecting step (1).And respectively according to the calculation formula (II) shown in above and (III), the calculating total conversion rate of hydrogen peroxide and the selectivity of propylene oxide, result is as shown in table 1.
Comparative example 2
According to the method identical with embodiment 1, prepare propylene oxide, difference is that the reactor using in step (1) is the slurry bed reactor with identical in step (2), the temperature of reaction is 85 ℃, pressure is 4MPa, time is 1 hour, by the amount of hydrogen peroxide in mixture after iodimetry,iodometry detection reaction, and by the amount of the propylene oxide of generation in chromatogram marker method detecting step (2), and by the amount of the middle total epoxide generating of chromatogram marker method detecting step (1).And respectively according to the calculation formula (II) shown in above and (III), the calculating total conversion rate of hydrogen peroxide and the selectivity of propylene oxide, result is as shown in table 1.
Embodiment 2
(1) HTS fine catalyst is loaded in moving-burden bed reactor (purchased from new capital, Chengdu Yong Tong machine works), the concentration of catalyzer in material is 5 % by weight.The first mixture that contains propylene, methyl alcohol, hydrogen peroxide is incorporated in moving-burden bed reactor, and wherein, in described the first mixture, the mol ratio of methyl alcohol, propylene and hydrogen peroxide is 4: 2: 1.The condition of described reaction comprises: temperature of reaction is 75 ℃, reaction pressure position 4MPa, time is 2 hours, with ammoniacal liquor, regulate the pH=7 of the first mixture material, by the amount of hydrogen peroxide in mixture after iodimetry,iodometry detection reaction, and according to the calculation formula (I) shown in above, calculate the transformation efficiency of hydrogen peroxide, result is as shown in table 1.And by the amount of the propylene oxide of generation in chromatogram marker method detecting step (1), and by the amount of the middle total epoxide generating of chromatogram marker method detecting step (1).
(2) reaction mixture step of 100 weight parts (1) being obtained and the HTS powder of 8 weight parts (Hunan Jian Chang company limited, HTS) be incorporated in slurry bed reactor (purchased from Tianjin Ao Zhan Science and Technology Ltd.) and carry out epoxidation reaction, the temperature of reaction is 40 ℃, the pressure of reaction is 1.5MPa, the time of reaction is 8 hours, by the amount of hydrogen peroxide in mixture after iodimetry,iodometry detection reaction, and by the amount of the propylene oxide of generation in chromatogram marker method detecting step (2), and by the amount of total epoxide of generation in chromatogram marker method detecting step (1).And respectively according to the calculation formula (II) shown in above and (III), the calculating total conversion rate of hydrogen peroxide and the selectivity of propylene oxide, result is as shown in table 1.
Embodiment 3
(1) HTS fine catalyst is loaded in moving-burden bed reactor (purchased from new capital, Chengdu Yong Tong machine works), the concentration of catalyzer in material is 5 % by weight.The first mixture that contains propylene, methyl alcohol, hydrogen peroxide is incorporated in moving-burden bed reactor, and wherein, in described the first mixture, the mol ratio of methyl alcohol, propylene and hydrogen peroxide is 6: 0.5: 1.The condition of described reaction comprises: temperature of reaction is 50 ℃, reaction pressure is 3MPa, time is 5 hours, with ammoniacal liquor, regulate the pH=6 of the first mixture material, by the amount of hydrogen peroxide in mixture after iodimetry,iodometry detection reaction, and according to the calculation formula (I) shown in above, calculate the transformation efficiency of the third hydrogen peroxide, result is as shown in table 1.And by the amount of the propylene oxide of generation in chromatogram marker method detecting step (1), and by the amount of the middle total epoxide generating of chromatogram marker method detecting step (1).
(2) reaction mixture step (1) being obtained is incorporated into knockout tower and carries out separation, the second logistics that obtains the first logistics that contains alkene and propylene oxide and contain unreacted hydrogen peroxide, solvent and water, detects the content of unreacted hydrogen peroxide in the second logistics by iodimetry,iodometry method.
(3) by the second logistics of 100 weight parts (in the second logistics, with respect to the unreacted hydrogen peroxide of 100 weight part, the propylene that adds 150 weight parts), the HTS powder of 5 weight parts (Hunan Jian Chang company limited, HTS) be incorporated in slurry bed reactor (purchased from Tianjin Ao Zhan Science and Technology Ltd.) and carry out epoxidation reaction, with ammoniacal liquor, regulate the pH=7 of material, the temperature of reaction is 45 ℃, the pressure of reaction is 2MPa, the time of reaction is 3 hours, by the amount of hydrogen peroxide in mixture after iodimetry,iodometry method detection reaction, and by the amount of the propylene oxide of generation in chromatogram marker method detecting step (2), and by the amount of total epoxide of generation in chromatogram marker method detecting step (1).And respectively according to the calculation formula (II) shown in above and (III), the calculating total conversion rate of hydrogen peroxide and the selectivity of propylene oxide, result is as shown in table 1.
Embodiment 4
(1) HTS fine catalyst is loaded in moving-burden bed reactor (purchased from new capital, Chengdu Yong Tong machine works), the concentration of catalyzer in material is 5 % by weight.The first mixture that contains propylene, methyl alcohol, hydrogen peroxide is incorporated in moving-burden bed reactor, and wherein, in described the first mixture, the mol ratio of methyl alcohol, propylene and hydrogen peroxide is 5: 1: 1.The condition of described reaction comprises: temperature of reaction is 40 ℃, reaction pressure is 2.5MPa, time is 5.5 hours, with ammoniacal liquor, regulate the pH=6 of the first mixture material, by the amount of hydrogen peroxide in mixture after iodimetry,iodometry method detection reaction, and according to the calculation formula (I) shown in above, calculate the transformation efficiency of hydrogen peroxide, result is as shown in table 1.And by the amount of the propylene oxide of generation in chromatogram marker method detecting step (1), and by the amount of the middle total epoxide generating of chromatogram marker method detecting step (1).
(2) reaction mixture step of 100 weight parts (1) being obtained is (in reaction mixture, with respect to the unreacted hydrogen peroxide of 100 weight part, the propylene that adds 100 weight parts) and the HTS powder of 6 weight parts (Hunan Jian Chang company limited, HTS) be incorporated in slurry bed reactor (purchased from Tianjin Ao Zhan Science and Technology Ltd.) and carry out epoxidation reaction, the temperature of reaction is 55 ℃, the pressure of reaction is 2.3MPa, the time of reaction is 5.5 hours, by the amount of hydrogen peroxide in mixture after iodimetry,iodometry method detection reaction, and by the amount of the propylene oxide of generation in chromatogram marker method detecting step (2), and by the amount of total epoxide of generation in chromatogram marker method detecting step (1).And respectively according to the calculation formula (II) shown in above-(IV), calculate the yield of the transformation efficiency of hydrogen peroxide, the selectivity of propylene oxide and propylene oxide, result is as shown in table 1.
Table 1
From the data of upper table 1, can find out, method provided by the invention is by being used the combination of moving-burden bed reactor and slurry bed reactor, can make the hydrogen peroxide using in reaction there is higher total conversion rate, and it is very low that the probability of side reaction occurs, can keep the selectivity of higher propylene oxide.
By embodiment 1 can be found out with comparative example 1 and comparative example 2 contrasts, use the combination of moving-burden bed reactor and slurry bed reactor, can overcome the shortcoming of the low conversion rate of the hydrogen peroxide existing while only using moving-burden bed reactor to react, also can overcome the low shortcoming of selectivity of the propylene oxide existing while only using slurry bed reactor to react simultaneously, and without using the too much reactor of series connection, reduced equipment cost.
Claims (9)
1. an olefin epoxidation process, wherein, the method comprises the following steps:
(1) under the condition of epoxidation reaction of olefines, under the existence of the first solid catalyst, make the first mixture that contains solvent, alkene and hydrogen peroxide in moving-burden bed reactor, carry out epoxidation reaction, the degree of reaction reaches more than 50% the transformation efficiency of hydrogen peroxide;
(2) under the condition of epoxidation reaction of olefines, the reaction mixture that step (1) is obtained and the second solid catalyst are incorporated in slurry bed reactor and carry out epoxidation reaction, and the degree of reaction reaches more than 95% the total conversion rate of hydrogen peroxide.
2. method according to claim 1, wherein, the mol ratio of described solvent, alkene and hydrogen peroxide is 4-15:0.5-5:1.
3. method according to claim 1 and 2, wherein, described solvent is that water, acetonitrile and carbonatoms are at least one in the alcohol of 1-6, described alkene is that carbonatoms is the alkene of 2-8.
4. method according to claim 1 and 2, wherein, the reaction conditions in described moving-burden bed reactor comprises: temperature is 30-90 ℃, and pressure is 0.5-4.5MPa, and the time is 0.2-10 hour, and pH is 5-8.
5. method according to claim 1 and 2, wherein, the reaction conditions of described slurry bed reactor comprises: temperature is 30-90 ℃, pressure is 0.5-4.5MPa, time is 0.2-10 hour, the reaction mixture obtaining with respect to the step (1) of 100 weight parts, the consumption of described the second solid catalyst is 3-10 weight part.
6. method according to claim 1, wherein, described the first solid catalyst and the second solid catalyst HTS of respectively doing for oneself.
7. method according to claim 1, wherein, the method also comprises: carry out epoxidation reaction in entering slurry bed reactor before, the reaction mixture obtaining in step (1) is carried out to separation, obtain containing alkene and propylene oxide and do not contain the first logistics of hydrogen peroxide and the second logistics that contains unreacted hydrogen peroxide, solvent and water; And in the second logistics, introduce alkene and obtain the second mixture, afterwards the second mixture is incorporated in slurry bed reactor and is reacted.
8. method according to claim 7, wherein, with respect to the unreacted hydrogen peroxide of 100 weight parts, the amount of the alkene of introducing in the second logistics is 100-200 weight part.
9. method according to claim 1, wherein, the method also comprises: carry out epoxidation reaction in the reaction mixture that step (1) is obtained is incorporated into slurry bed reactor before, in the reaction mixture obtaining in described step (1), fill into alkene, the described amount that fills into alkene makes in described reaction mixture, with respect to the unreacted hydrogen peroxide of 100 weight parts, the content of alkene is 100-200 weight part.
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| CN201010511515.XA CN102442976B (en) | 2010-10-11 | 2010-10-11 | Olefin Epoxidation Method |
| KR1020137012119A KR101872391B1 (en) | 2010-10-11 | 2011-10-11 | Method for producing oxidized olefin through olefin epoxidation |
| EP11831926.8A EP2628735B1 (en) | 2010-10-11 | 2011-10-11 | Method for producing oxidized olefin through olefin epoxidation |
| US13/878,659 US8859791B2 (en) | 2010-10-11 | 2011-10-11 | Process for producing an alkylene oxide by olefin epoxidation |
| PCT/CN2011/001703 WO2012048529A1 (en) | 2010-10-11 | 2011-10-11 | Method for producing oxidized olefin through olefin epoxidation |
| RU2013120981/04A RU2567749C2 (en) | 2010-10-11 | 2011-10-11 | Method of producing alkylene oxide by olefin epoxidation |
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| CN104311512B (en) * | 2014-10-13 | 2016-06-29 | 东南大学 | A kind of clean method for preparing of 1,2-epoxy butane |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1449392A (en) * | 2000-06-28 | 2003-10-15 | 索尔维公司 | Oxirane production using a peroxidized compound |
| US20040167234A1 (en) * | 2003-02-24 | 2004-08-26 | Syntroleum Corporation | Integrated fischer-tropsch process with improved alcohol processing capability |
| US20040176654A1 (en) * | 2003-03-07 | 2004-09-09 | Syntroleum Corporation | Linear alkylbenzene product and a process for its manufacture |
| CN1671678A (en) * | 2002-07-29 | 2005-09-21 | 巴斯福股份公司 | Process for producing propylene oxide using a reactor comprising multiple feed points and/or outlets |
| CN101279959A (en) * | 2008-05-21 | 2008-10-08 | 湖南长岭石化科技开发有限公司 | Method for synthesizing epoxypropane |
| CN101314596A (en) * | 2007-05-31 | 2008-12-03 | 中国石油化工股份有限公司 | A method for continuous production of propylene oxide |
-
2010
- 2010-10-11 CN CN201010511515.XA patent/CN102442976B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1449392A (en) * | 2000-06-28 | 2003-10-15 | 索尔维公司 | Oxirane production using a peroxidized compound |
| CN1671678A (en) * | 2002-07-29 | 2005-09-21 | 巴斯福股份公司 | Process for producing propylene oxide using a reactor comprising multiple feed points and/or outlets |
| US20040167234A1 (en) * | 2003-02-24 | 2004-08-26 | Syntroleum Corporation | Integrated fischer-tropsch process with improved alcohol processing capability |
| US20040176654A1 (en) * | 2003-03-07 | 2004-09-09 | Syntroleum Corporation | Linear alkylbenzene product and a process for its manufacture |
| CN101314596A (en) * | 2007-05-31 | 2008-12-03 | 中国石油化工股份有限公司 | A method for continuous production of propylene oxide |
| CN101279959A (en) * | 2008-05-21 | 2008-10-08 | 湖南长岭石化科技开发有限公司 | Method for synthesizing epoxypropane |
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