CN104926606A - Method for purifying recycle alcohol solvent of olefin epoxidation process and olefin epoxidation method - Google Patents
Method for purifying recycle alcohol solvent of olefin epoxidation process and olefin epoxidation method Download PDFInfo
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Abstract
The present invention provides a method for purifying a recycle alcohol solvent of olefin epoxidation process, and the method is as follows: hydrogen is sent into the recycle alcohol solvent by holes with the average pore size in nanoscale to obtain a hydrogen-containing recycle alcohol solvent; and the hydrogen-containing recycle alcohol solvent is sent into a tubular fixed bed reactor in the upward flowing manner for contact with a catalytic hydrogenation catalyst under the condition of liquid phase hydrogenation processing. The present invention also provides an olefin epoxidation method using the method for purifying. The method for purifying can effectively reduce the dosage of hydrogen without maintaining of recycle hydrogen in the reactor, the demand for a hydrogen recycle device is eliminated, the hydrogenation reaction process is simplified, the equipment investment and operation cost can be greatly reduced, and the operation can be performed under high space velocity. By adoption of the method for purifying of the recycle alcohol solvent, the method has good hydrogenation effect on a variety of impurities in the recycle alcohol solvent, and a high purity recycle alcohol solvent can be obtained.
Description
Technical field
The present invention relates to a kind of method of the recovery alcoholic solvent from epoxidation reaction of olefines process being carried out to purifying, the invention still further relates to a kind of olefin epoxidation process.
Background technology
Along with the development of petrochemical complex and fine chemistry industry, oxygen-containing organic compound has become very important intermediate.Being oxygenant with hydrogen peroxide, is solvent with low-carbon alcohol, and being catalyst alkene epoxidation with HTS thus preparing the requirement that oxygen-containing organic compound meets Green Chemistry and atom economy idea of development, is a kind of novel environment-friendly process having development prospect.In the process, solvent generally recycles.
But, olefin epoxidation process not only produces carbonyl compound, impurity such as acetal (ketone) compound and nitrogenous compound etc. in the reaction and separation processes stage, and reclaiming the high temperature rectifying recovery stage of alcoholic solvent, unreacted completely hydrogen peroxide and organic per-compounds also can the material such as oxidation solvent, produces the impurity such as carbonyl compound equally.For epoxidation of propylene technique, some materials in these impurity, as formaldehyde, acetaldehyde, propionic aldehyde, acetone, methyl-formiate, Methylal(dimethoxymethane), 1,1-glycol dimethyl ether, 1,1-Propanal dimethyl acetal, 2,2-Propanal dimethyl acetal, acetonitrile, Nitromethane 99Min. and nitroethane etc. are all difficult to be separated from recovery alcoholic solvent and product propylene oxide by rectifying, thus the recirculation purity drop reclaiming alcoholic solvent is caused, in product propylene oxide, impurities accumulation increases, thus have impact on quality product.Meanwhile, these impurity also can cause catalyst deactivation, affect catalyst activity, selectivity and life-span.Therefore, removing and reclaim impurity in alcoholic solvent and hydrogen peroxide is even more important to optimizing epoxidation of propylene technique, is the indispensable branch of olefin epoxidation process.
At present, to reclaiming the purification process of alcoholic solvent mainly based on reductive agent process, alkaline purification or directly rectifying, but these methods can only remove several impurity single or few in number mostly, its circulating solvent foreign matter content reclaimed will constantly accumulate, and will deepen gradually quality product, catalyst activity, selectivity and the impact in life-span.Therefore, most preferred recovery alcoholic solvent purification process is hydrogenation method of purification, the method can make the impurity of catalyst deactivation change with the impurity affecting quality product, change the material be easily separated with methanol rectification into, thus reduce the accumulation of reclaiming impurity in alcoholic solvent, reaching purifies reclaims the effect of alcoholic solvent.
Existing hydrogenation purification process adopts trickle bed hydrogenation technique usually, but this technique air speed is lower, and hydrogen usage is larger, need recycle hydrogen and the corresponding recycle system, make the volume of hydrogenation reaction device comparatively huge on the one hand, also improve cost of investment and the operation energy consumption of hydrogenation reaction device on the other hand.
Summary of the invention
The object of the invention is to overcome in existing epoxidation reaction of olefines process and reclaim alcoholic solvent when adopting catalytic hydrogenation process to carry out purifying, need recycle hydrogen and the corresponding recycle system thereof, make the volume of hydrogenation reaction device comparatively huge, facility investment running cost is high, and the technical problem that air speed is low, a kind of method of recovery alcoholic solvent being carried out to purifying is provided, the method hydrogen usage is little, without the need to recycle hydrogen, thus the demand eliminated for hydrogen gas circulating system, simplify hydrogenation reaction device, reduce facility investment and running cost, and can operate at a high space velocity.
According to a first aspect of the invention, the invention provides a kind of method of the recovery alcoholic solvent from epoxidation reaction of olefines process being carried out to purifying, the method comprises: the hole by mean pore size being nano-scale, by hydrogen feeding recovery alcoholic solvent, obtains containing hydrogen retrieval alcoholic solvent; Send in tubular reactor containing hydrogen retrieval alcoholic solvent in the mode upwards flowed by described, with the catalyst exposure with catalytic hydrogenation be seated in described tubular reactor under liquid-phase hydrogenatin treatment condition.
According to a second aspect of the invention, the invention provides a kind of olefin epoxidation process, the method comprises:
(1) under alkene epoxidation condition, at least one alkene, at least one superoxide are contacted with at least one HTS with at least one alcohol as solvent, obtains the liquid reaction mixture containing epoxide;
(2) described liquid reaction mixture is separated, obtains epoxide and reclaim alcoholic solvent;
(3), after adopting purification process provided by the invention to carry out purifying to described recovery alcoholic solvent, be circulated in step (1) as at least part of described solvent.
Hydrogen is injected by the through hole that mean pore size is nano-scale and reclaims alcoholic solvent by method according to the present invention, hydrogen high dispersing also can be dissolved at faster speed, be dispersed in and reclaim in alcoholic solvent, and carry out hydrogenation reaction by sending in tubular reactor in the mode upwards flowed containing hydrogen retrieval alcoholic solvent, hydrogen can be guaranteed with longer time stable existence in liquid phase, hydrogenation reaction can be carried out in the liquid phase, improve the effective rate of utilization of hydrogen on the one hand, reduce hydrogen usage; Eliminate the demand for hydrogen circulation device on the other hand, effectively simplify hydrogenation reaction technique, significantly reduce facility investment and running cost, and improve hydrogenation reaction speed, guarantee that device can run at a high space velocity.
Adopt method of the present invention to carry out purifying to recovery alcoholic solvent, to the plurality of impurities reclaimed in alcoholic solvent, all there is good hydrogenation effect, thus obtain highly purified recovery alcoholic solvent.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and forms a part for specification sheets, is used from explanation the present invention, but is not construed as limiting the invention with embodiment one below.
Fig. 1 is used for schematically illustrating a kind of preferred implementation of the component of adjacent fluid passage and gas passage in the gas liquid mixer that the present invention uses.
Fig. 2 is a kind of cross sectional representation of the component shown in Fig. 1.
Fig. 3 is the another kind of cross sectional representation of the component shown in Fig. 1.
Fig. 4 is the structural representation of the gas liquid mixer that the present invention uses.
Fig. 5 is a kind of embodiment of purification process provided by the invention.
Fig. 6 is the another kind of embodiment of purification process provided by the invention.
Fig. 7 is another embodiment of purification process provided by the invention.
Fig. 8 is for illustration of the annexation between gas liquid mixer and tubular reactor.
Description of reference numerals
1: passage 2: tube wall
3: porous-film 4: for the component of adjacent fluid passage and gas passage
5: housing 6: gas inlet
7: liquid inlet 8: liquid exit
9: gas liquid mixer 10: hydrogen
11: reclaim alcoholic solvent 12: tubular reactor
13: ring flange 14: ring flange
15: ring flange 16: ring flange
Embodiment
According to a first aspect of the invention, the invention provides a kind of method of the recovery alcoholic solvent from epoxidation reaction of olefines process being carried out to purifying, the method comprises: the hole by mean pore size being nano-scale, by hydrogen feeding recovery alcoholic solvent, obtains containing hydrogen retrieval alcoholic solvent; Send in tubular reactor containing hydrogen retrieval alcoholic solvent in the mode upwards flowed by described, with the catalyst exposure with catalytic hydrogenation be seated in described tubular reactor under liquid-phase hydrogenatin treatment condition.
In the present invention, described mean pore size is the mean pore size in the hole of nano-scale can be generally 1nm to 1000nm, is preferably 30nm to 1000nm, is more preferably 30nm to 800nm, more preferably 30nm to 500nm.Described mean pore size adopts scanning electron microscope method to measure.
Various method can be adopted to be injected by the hole that mean pore size is nano-scale by hydrogen and to reclaim alcoholic solvent.
In the preferred embodiment of the present invention, hydrogen is injected into by a kind of gas liquid mixer and reclaims in alcoholic solvent, described gas liquid mixer comprises at least one and reclaims the fluid passage of alcoholic solvent and at least one is for holding the gas passage of hydrogen for holding, adjoined by a component between described fluid passage and described gas passage, described component at least part of for there being porose area, described have porose area to have hole that described mean pore size is nano-scale, hydrogen is injected into by the hole that described mean pore size is nano-scale and reclaims in alcoholic solvent.In the present invention, term " fluid passage " refers to the space that can hold and reclaim alcoholic solvent; Term " gas passage " refers to the space that can hold hydrogen.
Described component at least part of for there being porose area, described in have porose area to extend along the length direction of described component.Preferably, porose area is had to cover whole component (that is, be that the component in the hole of nano-scale adjoins by having described mean pore size between described fluid passage and described gas passage, hydrogen is injected into by described hole and reclaims in alcoholic solvent) described in.Described have porose area to have hole that described mean pore size is nano-scale, with make hydrogen pass through described in there is hole that mean pore size is nano-scale be injected into and reclaim in alcoholic solvent.
Described component can make to be contained in hydrogen in described gas passage and is the hole of nano-scale and the component entered in the recovery alcoholic solvent be contained in fluid passage by described mean pore size for various.In an example, described component is formed by porous material, and the mean pore size in hole is wherein nano-scale.In another example, described component comprises matrix and attachment porous-film on the matrix, described matrix has through hole, described porous-film can be positioned on the surface contacted with the recovery alcoholic solvent being contained in described fluid passage of described matrix, also can be positioned on the surface contacted with the hydrogen being contained in described gas passage of described matrix.Preferably, described porous-film is positioned on the surface contacted with the recovery alcoholic solvent being contained in described fluid passage of described matrix.The hole of to be previously described mean pore size be the hole in described porous-film nano-scale.The mean pore size of the through hole on described matrix is not particularly limited, as long as can by gas.Preferably, the mean pore size of the through hole on described matrix is 1nm to 1000 μm (as 50-200 μm).
The shape of described component can be selected according to the position relationship of fluid passage and gas passage, is as the criterion by this component is adjacent can make described fluid passage and described gas passage.
In one embodiment of the invention, described component is the pipeline with at least one passage.The tube wall of described pipeline has through hole, and the mean pore size of described through hole is previously described nano-scale.
In another embodiment of the invention, described component is the pipeline with at least one passage, the inwall of the passage of described pipeline and/or the outer wall of pipeline adhere to by porous-film, the tube wall of described pipeline has through hole, the hole of to be mean pore size be the hole on described porous-film nano-scale, is called film pipe by the component with this structure below.Particularly, as Figure 1-3, described component is the film pipe with at least one passage.Described film pipe has the pipeline of through hole as matrix on tube wall 2, and described pipeline has at least one passage 1, and the inwall of passage 1 of described pipeline and/or the outer wall of pipeline are attached with porous-film 3.The mean pore size of the through hole on tube wall 2 is not particularly limited, as long as hydrogen can be made to pass through, can be generally 1nm to 1000 μm (as 50-200 μm); The hole of to be previously described mean pore size be the hole on described porous-film nano-scale.
In above-mentioned two kinds of embodiments, the quantity of the passage on described pipeline or described film pipe is preferably at least two, as 4-20 bar.
In actual mechanical process, described gas liquid mixer can also comprise housing, and the inside of described housing is provided with pipeline described at least one, Existential Space between the outer wall of described pipeline and the inwall of described housing.Particularly, as shown in Figure 4, component 4 can with housing 5 with the use of.That is, at least one component 4 is placed in housing 5, and makes Existential Space between the outer wall of component 4 and the inwall of housing 5.Passage on described component is as the described fluid passage for holding recovery alcoholic solvent, and the space that the outer wall of described component and the inwall of described housing are formed is as the described gas passage for holding hydrogen; Or the passage on described component is as the described gas passage for holding hydrogen, and the space that the outer wall of described component and the inwall of described housing are formed is as holding the described fluid passage reclaiming alcoholic solvent.Preferably, the passage on described component is as the described fluid passage for holding recovery alcoholic solvent, and the space that the outer wall of described component and the inwall of described housing are formed is as the described gas passage for holding hydrogen.
Passage is on the members as the described fluid passage for holding recovery alcoholic solvent, when the space that the outer wall of described component and the inwall of described housing are formed is as described gas passage for holding hydrogen, as shown in Figure 4, housing 5 has gas inlet 6, liquid inlet 7 and liquid exit 8, the two ends of described fluid passage are communicated with liquid exit 8 with liquid inlet 7 respectively, and described gas passage is communicated with gas inlet 6.Hydrogen is sent in housing 5 by gas inlet 6, sending into reclaiming alcoholic solvent in the passage of component 4, under the effect of pressure difference, hydrogen being entered in described recovery alcoholic solvent by the hole on tube wall, thus obtain containing hydrogen retrieval alcoholic solvent.
The filling ratio of described component in described housing can be generally that 20-70%(is as 40-60%).Described filling ratio refers to the percent value of the cubic capacity of the space that component occupies and housing.
The material forming described component can be inorganic materials (as inorganic ceramic), also can be organic materials, as long as the material forming described component with hydrogen and can not reclaim alcoholic solvent generation chemical interaction.
The amount sending into the hydrogen reclaimed in alcoholic solvent can be selected according to concrete reaction conditions.Hydrogen is sent into by the hole that mean pore size is nano-scale and is reclaimed in alcoholic solvent by method of the present invention, can make hydrogen high dispersing and be dissolved in reclaim in alcoholic solvent, thus provides enough hydrogen sources for hydrogenation reaction, and guarantees that hydrogenation reaction is carried out in the liquid phase.Therefore, even if method of the present invention does not send into hydrogen in a large number in recovery alcoholic solvent, simultaneously without the need to maintaining certain hydrogen dividing potential drop in the reactor, good hydrotreatment effect can also be obtained.According to the inventive method, the injection rate of hydrogen is under described liquid-phase hydrogenatin treatment condition, and the 0.8-1.5 of the saturated meltage of hydrogen in described recovery alcoholic solvent doubly.Described saturated meltage refers under liquid-phase hydrogenatin treatment condition, is dissolved in the grams that 100g reclaims the hydrogen in alcoholic solvent.The various methods that this area can be adopted to commonly use are to determine that hydrogen is reclaiming the saturated meltage in alcoholic solvent, repeats no more herein.
According to method of the present invention, preferably hydrogen is sent into temperature and pressure be in hydrogenation temperature and hydrogenation pressure under recovery alcoholic solvent in, hydrogen can be reduced so further from containing the trend of overflowing hydrogen retrieval alcoholic solvent.Particularly, hydrogen can be sent into temperature and be 80-150 DEG C and pressure is that 1.5-4MPa(is in gauge pressure) recovery alcoholic solvent in.
Described tubular reactor refers to the reactor had compared with larger ratio of height to diameter.Particularly, the height of described tubular reactor and the ratio (that is, aspect ratio) of internal diameter can be 10-200:1.The internal diameter of described tubular reactor can be conventional selection, such as, can be 200-2000mm.Compared with tank reactor, adopt tubular reactor can reduce the volume of reactor on the one hand further, on the other hand when by previously described gas liquid mixer (be particularly pipeline or film pipe at described component), directly described gas liquid mixer is arranged on the material inlet pipeline of described tubular reactor, flexible operation and convenient.
According to method of the present invention, the described hydrogen retrieval alcoholic solvent that contains is admitted in described tubular reactor in the mode upwards flowed.Can by sending into described from the bottom of described tubular reactor containing hydrogen retrieval alcoholic solvent, with the catalyst exposure with catalytic hydrogenation be seated in the beds of described tubular reactor, and export reclaiming alcoholic solvent after contacting the hydrogenation that obtains from the top of described tubular reactor.
The described contact containing hydrogen retrieval alcoholic solvent and catalyzer can be carried out under the hydroprocessing temperature of routine and pressure, is not particularly limited.Usually, the described hydrogen retrieval alcoholic solvent that contains is comprised with the condition of the catalyst exposure with catalytic hydrogenation: temperature can be 80-150 DEG C; In gauge pressure, the pressure in reactor can be 1.5-4MPa; Volume space velocity containing hydrogen retrieval alcoholic solvent can be 5-15h
-1.
According to method of the present invention, the quantity of described tubular reactor can be 1, also can be more than 2.When the quantity of described tubular reactor is more than 2, described tubular reactor can, for being connected in series, can, for being connected in parallel, can also be also series connection and combination in parallel.Described be connected in series the hydrogenation referring to that previous tubular reactor exports after logistics be the charging of next tubular reactor; Described being connected in parallel refers to do not have material to exchange between tubular reactor.
Adopt previously described gas liquid mixer to be injected by hydrogen and reclaim alcoholic solvent, to obtain containing hydrogen retrieval alcoholic solvent, and will containing hydrogen retrieval alcoholic solvent feeding tubular reactor time, described gas liquid mixer is r for the internal diameter exported containing the outlet of hydrogen retrieval alcoholic solvent
1, described tubular reactor is r for the internal diameter inputted containing the entrance of hydrogen retrieval alcoholic solvent
2, preferably, r
1/ r
2=0.6-1(is as 0.85-1).The internal diameter connecting the pipe of described outlet and described entrance is r
3, preferably, r
1/ r
3=0.85-1.5(is as 0.85-1).Hydrogeneous like this recycle alcohol solvent is more stable in transport process, thus can obtain better hydrogenation effect.
It is a kind of preferred implementation according to method of the present invention shown in Fig. 5.In this embodiment, in gas liquid mixer 9, hydrogen 10 is injected and reclaim alcoholic solvent 11, obtain containing hydrogen retrieval alcoholic solvent.Enter in tubular reactor 12 containing hydrogen retrieval alcoholic solvent and there is the catalyst exposure of catalytic hydrogenation, thus carrying out hydrogenation reaction, after obtaining hydrogenation, reclaiming alcoholic solvent.
According to this embodiment, can arrange multiple tubular reactor, can, for being connected in series, can, for being connected in parallel, can also be also series connection and combination in parallel between multiple tubular reactor.When multiple tubular reactor is connected in series, along the flow direction of material, gas liquid mixer can be arranged on the inlet end of first tubular reactor; Also as shown in Figure 6, gas liquid mixer 9 can be set respectively at the inlet end of each tubular reactor 12.When multiple tubular reactor is connected in parallel, a gas liquid mixer only can be set, alcoholic solvent will be reclaimed and mix with hydrogen, then send in the multiple tubular reactors be connected in parallel by what obtain respectively containing hydrogen retrieval alcoholic solvent; Also as shown in Figure 7 gas liquid mixer 9 can be set respectively at the inlet end of each tubular reactor 12.
Can adopt and in various manners gas liquid mixer is connected on entrance pipe, such as: a ring flange (Fig. 8 shows one of them ring flange 13) respectively can be set at the two ends of gas liquid mixer, be connected with the flangeseal on corresponding entrance pipe separately (as shown in Figure 8, the ring flange 13 of gas liquid mixer one end is tightly connected with the ring flange 14 on entrance pipe); The other end of entrance pipe is connected with the ring flange 16 of the inlet end of tubular reactor 12 by ring flange 15.
Method of the present invention is not particularly limited for the described kind with the catalyzer of catalytic hydrogenation, can be conventional selection.Preferably, the described catalyzer with catalytic hydrogenation comprises carrier and load activeconstituents on the carrier and auxiliary agent, in the total amount of described catalyzer for benchmark and with element, the content of described activeconstituents is 5-20 % by weight, the content of described auxiliary agent is 0.5-5 % by weight, the content of described carrier is 75-94.5 % by weight, and described activeconstituents is Ni and/or Co, and described auxiliary agent is Ti.
Described carrier can be common porous heat-resistant inorganic oxide, such as silicon oxide and/or aluminum oxide.Described carrier be silicon oxide and aluminum oxide time, the ratio between silicon oxide and aluminum oxide is not particularly limited, but the weight ratio of silicon oxide and aluminum oxide is preferably 0.5-1.5:1.
The method that this catalyzer can adopt field of catalyst preparation conventional obtains, as pickling process, spraying process or liquid phase deposition.
With adopt the precious metals such as such as Ru or Pd as active ingredient catalyzer compared with, this catalyzer not only cost is more cheap, and for good hydrogenation effect can also be obtained in method of the present invention, wherein, hydrogenation hydrogenation ratio for the hydrogen peroxide reclaimed in alcoholic solvent and organo-peroxide can reach 100%, hydrogenation hydrogenation ratio for carbonyl compound can reach more than 95%, hydrogenation hydrogenation ratio for acetal (ketone) compound can reach more than 70%, hydrogenation hydrogenation ratio for nitrogenous compound can reach more than 97%, recovery alcoholic solvent after hydrogenation can reach more than 99% through its determining alcohol of simple rectifying.
Can also comprise according to method of the present invention and carry out rectifying and collect alcohol cut reclaiming alcoholic solvent after the hydrogenation obtained with the catalyst exposure with catalytic hydrogenation, to improve the purity of the recovery alcoholic solvent obtained further.The present invention is not particularly limited for the condition of described rectifying, can carry out under normal conditions.Usually, described rectifying can be atmospheric distillation.
According to purification process of the present invention, described recovery alcoholic solvent comes from epoxidation reaction of olefines process, is remaining solution isolate epoxide from the reaction mixture that epoxidation reaction of olefines process obtains after.Described olefin epoxidation process is generally under epoxidation reaction condition, using HTS as catalyzer, using low-carbon alcohol as solvent, using superoxide as oxygenant by alkene epoxidation.That is, described mixture is generally under epoxidation reaction condition, at least one alkene, at least one superoxide is obtained with contacting as at least one alcohol of solvent with at least one HTS.
The various molecular sieves that described HTS can be replaced by titanium atom for the part Siliciumatom in skeleton structure and be formed, preferably there is the HTS of MFI structure, there is the HTS of MWW structure, there is the HTS of MCM structure and have in the HTS of BETA structure one or more.More preferably, described HTS is the HTS with MFI structure.
Described low-carbon alcohol can be the fatty alcohol of 1-6 for carbonatoms, such as: methyl alcohol, ethanol, propyl alcohol and isomer thereof, butanols and isomer, amylalcohol and isomer thereof and hexanol and isomer thereof.Preferably, described solvent is methyl alcohol.
Described alkene can for being selected from the alkene that carbonatoms is 2-8, such as: propylene, butylene and isomer thereof, amylene and isomer, hexene and isomer thereof, heptene and isomer thereof and octene and isomer thereof.Preferably, described alkene is propylene.
Described superoxide refers to the compound containing-O-O-key in molecular structure, can be one or more in hydrogen peroxide, organo-peroxide and peracid.Preferably, described superoxide is hydrogen peroxide.
Described epoxidation reaction is preferably carried out in fixed-bed reactor.
Described epoxidation reaction condition well known to a person skilled in the art, such as, the temperature of described contact can be 30-150 DEG C, can be that 0.5-4.5MPa(is in gauge pressure at pressure) and the pH of reaction system be 5-8 under carry out described contact, during liquid, volume space velocity can be 0.1-7h
-1.The mol ratio of solvent, alkene and hydrogen peroxide can be (4-15): (1-5): 1.
Adopt method of the present invention to carry out purifying to described recovery alcoholic solvent, to the plurality of impurities reclaimed in alcoholic solvent, all there is good hydrogenation effect, thus obtain the high recovery alcoholic solvent of purity.
Purification process of the present invention is particularly suitable for combinationally using with epoxidation reaction of olefines process, after the recovery alcoholic solvent purifying from epoxidation reaction of olefines process is also optionally carried out rectifying, as solvent cycle in epoxidation reaction of olefines process.
Thus, according to a second aspect of the invention, present invention also offers a kind of olefin epoxidation process, the method comprises:
(1) under alkene epoxidation condition, at least one alkene, at least one superoxide are contacted with at least one HTS with at least one alcohol as solvent, obtains the liquid reaction mixture containing epoxide;
(2) described liquid reaction mixture is separated, obtains epoxide and reclaim alcoholic solvent;
(3), after adopting purification process provided by the invention to carry out purifying to described recovery alcoholic solvent, be circulated in step (1) as at least part of described solvent.
Described epoxidation reaction of olefines process and being described in detail above reclaiming the method that alcoholic solvent carries out purifying, no longer describes in detail herein.
The method that the present invention is separated for the liquid reaction mixture obtained epoxidation reaction is not particularly limited, and can be conventional selection, as long as epoxide can be separated from described liquid reaction mixture.Such as: can be separated described liquid mixture by rectificating method, obtain epoxide and reclaim alcoholic solvent.Usually, described rectifying can be carried out under the pressure of 0.1-0.2MPa (in gauge pressure).
Describe the present invention in detail below in conjunction with embodiment and comparative example, but therefore do not limit the scope of the invention.
In following examples and comparative example, adopt vapor-phase chromatography method to analyze recovery alcoholic solvent and purified recovery alcoholic solvent, and calculate hydrogenation ratio.
In following examples and comparative example, scanning electron microscope method is adopted to measure mean pore size; If not otherwise specified, pressure is in gauge pressure.
Embodiment 1-7 is for illustration of method of the present invention.
Embodiment 1
(1) be loaded in the isothermal reaction district of fixed-bed tube reactor by 50g Ti-Si catalyst TS-1, catalyzer fills porcelain ring filler up and down, and makes whole reaction system stopping property intact.Make propylene and liquid stream enter reaction zone in the mode to upper reaches, carry out epoxidation reaction, obtain epoxidation reaction mixture.Wherein, in liquid stream, methyl alcohol: propylene: the mol ratio of hydrogen peroxide is 6:2:1, adds ammoniacal liquor in liquid stream, makes the pH of described liquid stream be 5.3.Controlling temperature of reaction is 40 DEG C, and reaction pressure is 2.5MPa, and liquid hourly space velocity is 1.5h
-1.
(2) epoxidation reaction mixture step (1) obtained is carry out rectifying under the condition of 0.15MPa at pressure, to isolate propylene oxide wherein, is recycled alcoholic solvent simultaneously.
(3) adopt the method for Fig. 5 to carry out hydrotreatment to the recovery alcoholic solvent that step (2) obtains, actual conditions is as follows.
By the gas liquid mixer shown in Fig. 4, hydrogen is sent in recovery alcoholic solvent, obtain containing hydrogen retrieval alcoholic solvent.Send into tubular reactor in the mode upwards flowed by described containing hydrogen retrieval alcoholic solvent (internal diameter is for 500mm, the aspect ratio of beds is 150:1) in there is the catalyst exposure of catalytic hydrogenation, carry out hydrogenation reaction, after obtaining hydrogenation, reclaim alcoholic solvent.
Wherein, the film pipe that gas liquid mixer comprises as shown in Figure 2 (is purchased from BeiJing ZhongTianYuan Environment Engineering Co., Ltd, pipeline is evenly distributed with 19 fluid passages, the internal diameter of each fluid passage is 3.3mm, the mean pore size in the hole on matrix is 100 μm, the mean pore size in the hole on porous-film is 500nm) and the housing (film pipe filling ratio is in the housing 60%) that uses with this tube fit, the space that the outer wall of pipeline and the inwall of housing are formed is gas passage.
Temperature in fluid passage is 120 DEG C, and pressure is 4MPa.
The ratio of the internal diameter of liquid material outlet of gas liquid mixer and the internal diameter of the material inlet of tubular reactor is 0.9, and the internal diameter of the liquid material outlet of gas liquid mixer is 1 with the ratio of the internal diameter of the pipeline of the material inlet of the material outlet and tubular reactor that are connected gas liquid mixer.
To inject the amount of hydrogen reclaiming alcoholic solvent be hydrogen is reclaiming 1.0 times of saturated meltage (at 120 DEG C and be 0.07g/100g under 4MPa) of alcoholic solvent.
There is the catalyzer of catalytic hydrogenation with SiO
2-Al
2o
3as carrier (SiO
2with Al
2o
3weight ratio be 1:1), using Ni as active ingredient, using Ti as auxiliary agent, wherein, in the total amount of catalyzer for benchmark and with element, the content of Ni is the content of 10 % by weight, Ti is 3 % by weight.
The condition of hydrogenation reaction comprises: the temperature in beds is 120 DEG C, and pressure is 4MPa, and during liquid, volume space velocity is 10h
-1.
(4) reclaim alcoholic solvent after the hydrogenation obtained step (3) at ambient pressure and carry out rectifying, collect the cut that boiling range is 65-70 DEG C, obtain purifying and reclaim alcoholic solvent, the purity that wherein hydrogenation ratio of various impurity and purifying reclaim alcoholic solvent is listed in Table 1.
Comparative example 1
The method identical with embodiment 1 is adopted to carry out epoxidation reaction of olefines and carry out purifying to the recovery alcoholic solvent obtained, unlike, the mean pore size in the hole on porous-film is 5 μm (being purchased from BeiJing ZhongTianYuan Environment Engineering Co., Ltd).Experimental result is listed in Table 1.
Comparative example 2
The method identical with embodiment 1 is adopted to carry out epoxidation reaction of olefines, unlike, the operation of step (3) is as follows:
Mixed with recovery alcoholic solvent by hydrogen with static mixer (purchased from the SV type static mixer of Qidong person of outstanding talent along many petrochemical equipments company limited), wherein, the feeding amount of hydrogen is 8 times of the saturated meltage of hydrogen in recovery alcoholic solvent.To send into what obtain in fixed-bed reactor under trickle bed hydrogenation process conditions containing hydrogen retrieval alcoholic solvent, carry out hydrotreatment.Wherein, temperature is 120 DEG C, and pressure is 4MPa, and during liquid, volume space velocity is 3h
-1.Experimental result is listed in Table 1.
Embodiment 2
(1) method identical with embodiment 1 is adopted to carry out epoxidation reaction.
(2) method identical with embodiment 1 is adopted to be recycled alcoholic solvent.
(3) in the recovery alcoholic solvent adopting the method identical with embodiment 1 to be obtained by hydrogen implantation step (2), unlike, the temperature in fluid passage is 150 DEG C, and pressure is 1.5MPa.To inject the amount of hydrogen reclaiming alcoholic solvent be hydrogen is reclaiming 1.0 times of saturated meltage (at 150 DEG C and be 0.05g/100g under 1.5MPa) of alcoholic solvent.
Sent in tubular reactor by the hydrogeneous recycle alcohol solvent obtained and carry out hydrotreatment, wherein, the difference of hydrotreatment and embodiment 1 is:
There is the catalyzer of catalytic hydrogenation with Al
2o
3as carrier, using Co as active ingredient, using Ti as auxiliary agent, wherein, in the total amount of catalyzer for benchmark and with element, the content of Co is the content of 5 % by weight, Ti is 3 % by weight;
Temperature in the beds of tubular reactor is 150 DEG C, and pressure is 1.5MPa, and during liquid, volume space velocity is 5h
-1.
(4) reclaim alcoholic solvent after the hydrogenation obtained step (3) at ambient pressure and carry out rectifying, collect the cut that boiling range is 65-70 DEG C, obtain purifying and reclaim alcoholic solvent, the purity that wherein hydrogenation ratio of various impurity and purifying reclaim alcoholic solvent is listed in Table 1.
Embodiment 3
(1) method identical with embodiment 1 is adopted to carry out epoxidation reaction.
(2) method identical with embodiment 1 is adopted to be recycled alcoholic solvent.
(3) in the recovery alcoholic solvent adopting the method identical with embodiment 1 to be obtained by hydrogen implantation step (2), unlike, the temperature in fluid passage is 140 DEG C, and pressure is 3.5MPa.To inject the amount of hydrogen reclaiming alcoholic solvent be hydrogen is reclaiming 1.0 times of saturated meltage (at 140 DEG C and be 0.07g/100g under 3.5MPa) of alcoholic solvent.
Sent in tubular reactor by the hydrogeneous recycle alcohol solvent obtained and carry out hydrotreatment, wherein, the difference of hydrotreatment and embodiment 1 is: have the catalyzer of catalytic hydrogenation with SiO
2as carrier, using Ni as active ingredient, using Ti as auxiliary agent, wherein, in the total amount of catalyzer for benchmark and with element, the content of Co is the content of 10 % by weight, Ti is 5 % by weight; Temperature in the beds of tubular reactor is 140 DEG C, and pressure is 3.5MPa, and during liquid, volume space velocity is 15h
-1.
(4) reclaim alcoholic solvent after the hydrogenation obtained step (3) at ambient pressure and carry out rectifying, collect the cut that boiling range is 65-70 DEG C, obtain purifying and reclaim alcoholic solvent, the purity that wherein hydrogenation ratio of various impurity and purifying reclaim alcoholic solvent is listed in Table 1.
Embodiment 4
Adopt the method identical with embodiment 1 to carry out epoxidation reaction and carry out purifying to reclaiming alcoholic solvent, unlike, the catalyzer with catalytic hydrogenation used in step (3) for Ru/C catalyzer (wherein, in the total amount of catalyzer for benchmark and with element, the content of Ru is 2 % by weight).Experimental result is listed in Table 1.
Comparative example 3
Adopt the method identical with comparative example 2 to carry out epoxidation reaction and carry out purifying to reclaiming alcoholic solvent, unlike, the catalyzer with catalytic hydrogenation that step (3) uses is identical with embodiment 4.Experimental result is listed in Table 1.
Table 1
From the results shown in Table 1, adopt method of the present invention to process recovery alcoholic solvent, effectively can carry out hydrogenation to the various impurity reclaimed in alcoholic solvent, obtain the recovery alcoholic solvent that purity is high.
Embodiment 1 and embodiment 4 are compared and can be found out, method of the present invention adopts non-precious metal catalyst, can obtain better hydrogenation effect, obtain the recovery alcoholic solvent that purity is more than 99%.
Embodiment 5
(1) be loaded in the isothermal reaction district of fixed-bed tube reactor by 50g Ti-Si catalyst TS-1, catalyzer fills porcelain ring filler up and down, and makes whole reaction system stopping property intact.Make propylene and liquid stream enter reaction zone in the mode to upper reaches, carry out epoxidation reaction, obtain epoxidation reaction mixture.Wherein, in liquid stream, methyl alcohol: propylene: the mol ratio of hydrogen peroxide is 4:1:1, adds ammoniacal liquor in liquid stream, makes the pH of described liquid stream be 5.Controlling temperature of reaction is 30 DEG C, and reaction pressure is 0.5MPa, and during liquid, volume space velocity is 0.1h
-1.
(2) epoxidation reaction mixture that step (1) obtains is separated under the rectifying condition of temperature 102 DEG C, pressure 0.15MPa, to isolate propylene oxide wherein, is recycled alcoholic solvent simultaneously.
(3) adopt the method for Fig. 5 to carry out hydrotreatment to the recovery alcoholic solvent that step (2) obtains, actual conditions is as follows.
By the gas liquid mixer shown in Fig. 4, hydrogen is sent in recovery alcoholic solvent, obtain containing hydrogen retrieval alcoholic solvent.Send into tubular reactor in the mode upwards flowed by described containing hydrogen retrieval alcoholic solvent (internal diameter is for 200mm, the aspect ratio of beds is 200:1) in there is the catalyst exposure of catalytic hydrogenation, carry out hydrogenation reaction, after obtaining hydrogenation, reclaim alcoholic solvent.
Wherein, the film pipe that gas liquid mixer comprises as shown in Figure 2 (is purchased from BeiJing ZhongTianYuan Environment Engineering Co., Ltd, pipeline is evenly distributed with 19 fluid passages, the internal diameter of each fluid passage is 3.3mm, the mean pore size in the hole on matrix is 100 μm, the mean pore size in the hole on porous-film is 30nm) and the housing (film pipe filling ratio is in the housing 50%) that uses with this tube fit, the space that the outer wall of pipeline and the inwall of housing are formed is gas passage.
Temperature in fluid passage is 80 DEG C, and pressure is 4.0MPa.
The ratio of the internal diameter of the internal diameter of the material outlet of gas liquid mixer and the material inlet of tubular reactor is 0.9, and the internal diameter of the material outlet of gas liquid mixer is 0.9 with the ratio of the internal diameter of the pipeline of the material inlet of the material outlet and tubular reactor that are connected gas liquid mixer.
To inject the amount of hydrogen reclaiming alcoholic solvent be hydrogen is reclaiming 1.5 times of saturated meltage (at 80 DEG C and be 0.04g/100g under 4MPa) of alcoholic solvent.
There is the catalyzer of catalytic hydrogenation with SiO
2as carrier, using Ni as active ingredient, using Ti as auxiliary agent, wherein, in the total amount of catalyzer for benchmark and with element, the content of Ni is the content of 20 % by weight, Ti is 0.5 % by weight.
The condition of hydrogenation reaction comprises: the temperature in beds is 80 DEG C, and pressure is 4MPa, and during liquid, volume space velocity is 5h
-1.
(4) reclaim alcoholic solvent after the hydrogenation obtained step (3) at ambient pressure and carry out rectifying, collect the cut that boiling range is 65-70 DEG C, obtain purifying and reclaim alcoholic solvent, the purity that wherein hydrogenation ratio of various impurity and purifying reclaim alcoholic solvent is listed in table 2.
Embodiment 6
(1) be loaded in the isothermal reaction district of fixed-bed tube reactor by 50g Ti-Si catalyst TS-1, catalyzer fills porcelain ring filler up and down, and makes whole reaction system stopping property intact.Make propylene and liquid stream enter reaction zone in the mode to upper reaches, carry out epoxidation reaction, obtain epoxidation reaction mixture.Wherein, in liquid stream, methyl alcohol: propylene: the mol ratio of hydrogen peroxide is 15:5:1, adds ammoniacal liquor in liquid stream, makes the pH of described liquid stream be 8.Controlling temperature of reaction is 90 DEG C, and reaction pressure is 4.5MPa, and during liquid, volume space velocity is 7h
-1.
(2) epoxidation reaction mixture that step (1) obtains is separated under the rectifying condition of temperature 102 DEG C, pressure 0.15MPa, to isolate propylene oxide wherein, is recycled alcoholic solvent simultaneously.
(3) adopt the method for Fig. 5 to carry out hydrotreatment to the recovery alcoholic solvent that step (2) obtains, actual conditions is as follows.
By the gas liquid mixer shown in Fig. 4, hydrogen is sent in recovery alcoholic solvent, obtain containing hydrogen retrieval alcoholic solvent.Send into tubular reactor in the mode upwards flowed by described containing hydrogen retrieval alcoholic solvent (internal diameter is for 2000mm, the aspect ratio of beds is 10:1) in there is the catalyst exposure of catalytic hydrogenation, carry out hydrogenation reaction, after obtaining hydrogenation, reclaim alcoholic solvent.
Wherein, the pipeline on the component tube wall of adjacent fluid passage and gas passage in gas liquid mixer with through hole (is purchased from BeiJing ZhongTianYuan Environment Engineering Co., Ltd, pipeline is evenly distributed with 19 fluid passages, the internal diameter of each fluid passage is 3.3mm, the mean pore size of the through hole on the tube wall of pipeline is 250nm) and the housing (pipeline filling ratio is in the housing 45%) that uses with this tube fit, the space that the outer wall of pipeline and the inwall of housing are formed is gas passage.
Temperature in fluid passage is 150 DEG C, and pressure is 4MPa.
The ratio of the internal diameter of the internal diameter of the material outlet of gas liquid mixer and the material inlet of tubular reactor is 0.9, and the internal diameter of the material outlet of gas liquid mixer is 0.9 with the ratio of the internal diameter of the pipeline of the material inlet of the material outlet and tubular reactor that are connected gas liquid mixer.
To inject the amount of hydrogen reclaiming alcoholic solvent be hydrogen is reclaiming 1.5 times of saturated meltage (at 150 DEG C and be 0.08g/100g under 4MPa) of alcoholic solvent.
There is the catalyzer of catalytic hydrogenation with SiO
2as carrier, using Ni as active ingredient, using Ti as auxiliary agent, wherein, in the total amount of catalyzer for benchmark and with element, the content of Ni is the content of 10 % by weight, Ti is 3 % by weight.
The condition of hydrogenation reaction comprises: the temperature in beds is 150 DEG C, and pressure is 4MPa, and during liquid, volume space velocity is 5h
-1.
(4) reclaim alcoholic solvent after the hydrogenation obtained step (3) at ambient pressure and carry out rectifying, collect the cut that boiling range is 65-70 DEG C, obtain purifying and reclaim alcoholic solvent, the purity that wherein hydrogenation ratio of various impurity and purifying reclaim alcoholic solvent is listed in table 2.
Embodiment 7
(1) adopt the method identical with embodiment 1 step (1) to carry out epoxidation reaction, obtain epoxidation reaction mixture.
(2) adopt the method identical with embodiment 1 step (1) to be separated epoxidation reaction mixture, be recycled alcoholic solvent.
(3) method identical with embodiment 1 step (3) is adopted to carry out hydrotreatment to the recovery alcoholic solvent that step (2) obtains, unlike:
Temperature in fluid passage is 140 DEG C, and pressure is 4MPa;
To inject the amount of hydrogen reclaiming alcoholic solvent be hydrogen is reclaiming 0.8 times of saturated meltage (at 140 DEG C and be 0.07g/100g under 4MPa) of alcoholic solvent;
There is the catalyzer of catalytic hydrogenation with SiO
2as carrier, using Ni as active ingredient, using Ti as auxiliary agent, wherein, in the total amount of catalyzer for benchmark and with element, the content of Ni is the content of 10 % by weight, Ti is 3 % by weight.
(4) reclaim alcoholic solvent after the hydrogenation obtained step (3) at ambient pressure and carry out rectifying, collect the cut that boiling range is 65-70 DEG C, obtain purifying and reclaim alcoholic solvent, the purity that wherein hydrogenation ratio of various impurity and purifying reclaim alcoholic solvent is listed in table 2.
Table 2
| Hydrogenation ratio (%) | Embodiment 5 | Embodiment 6 | Embodiment 7 |
| Hydrogen peroxide and organic per-compounds | 100 | 100 | 100 |
| Carbonyl compound | 95.2 | 96.5 | 98.5 |
| Acetal (ketone) | 71.3 | 74.7 | 77.4 |
| Nitrogenous compound | 98.3 | 98.1 | 99.1 |
| Purity | 99.1 | 99.2 | 99.5 |
The result of embodiment 5-7 confirms, adopts method of the present invention to process recovery alcoholic solvent, effectively can carry out hydrogenation to the various impurity reclaimed in alcoholic solvent, obtain the recovery alcoholic solvent that purity is high.
Claims (23)
1. the recovery alcoholic solvent from epoxidation reaction of olefines process is carried out to a method for purifying, the method comprises: the hole by mean pore size being nano-scale, by hydrogen feeding recovery alcoholic solvent, obtains containing hydrogen retrieval alcoholic solvent; Send in tubular reactor containing hydrogen retrieval alcoholic solvent in the mode upwards flowed by described, with the catalyst exposure with catalytic hydrogenation be seated in described tubular reactor under liquid-phase hydrogenatin treatment condition.
2. method according to claim 1, hydrogen is injected described recovery alcoholic solvent by a kind of gas liquid mixer, thus obtain described containing hydrogen retrieval alcoholic solvent, described gas liquid mixer comprises at least one for holding the fluid passage of described recovery alcoholic solvent and at least one is for holding the gas passage of described hydrogen, adjoined by a component between described fluid passage and described gas passage, described component at least part of for there being porose area, described have porose area to have hole that described mean pore size is nano-scale, described hydrogen is injected in described recovery alcoholic solvent by the hole that described mean pore size is nano-scale.
3. method according to claim 2, wherein, described component is the pipeline with at least one passage, and the tube wall of described pipeline has through hole, the hole of described through hole to be mean pore size be nano-scale; Or the inwall of the passage of described pipeline and/or the outer wall of pipeline are attached with porous-film, and the tube wall of described pipeline has through hole, the hole of to be mean pore size be the hole on described porous-film nano-scale.
4. method according to claim 3, wherein, described gas liquid mixer also comprises housing, described housing has gas inlet, liquid inlet and liquid exit, the inside of described housing is provided with pipeline described at least one, Existential Space between the outer wall of described pipeline and the inwall of described housing, passage on described pipeline is as described fluid passage, the space that the outer wall of described pipeline and the inwall of described housing are formed is as described gas passage, the two ends of described fluid passage are communicated with described liquid exit with described liquid inlet respectively, described gas passage is communicated with described gas inlet.
5. according to the method in claim 2-4 described in any one, wherein, described gas liquid mixer is arranged on the inlet end of described tubular reactor.
6. according to the method in claim 1-4 described in any one, wherein, mean pore size is the mean pore size in the hole of nano-scale is 30-1000nm.
7. according to the method in claim 1-4 described in any one, wherein, the injection rate of hydrogen is under described liquid-phase hydrogenatin treatment condition, and the 0.8-1.5 of the saturated meltage of hydrogen in described recovery alcoholic solvent doubly.
8. method according to claim 1, wherein, described recovery alcoholic solvent is from remaining solution after epoxidation reaction of olefines obtains deviating from epoxide mixture.
9. method according to claim 8, wherein, described mixture is under epoxidation reaction condition, at least one alkene, at least one superoxide is obtained with contacting as at least one alcohol of solvent with at least one HTS.
10. method according to claim 9, wherein, described alkene epoxidation condition comprises: the mol ratio of solvent, alkene and hydrogen peroxide is (4-15): (1-5): 1; Temperature is 30-150 DEG C; In gauge pressure, pressure is 0.5-4.5MPa; During liquid, volume space velocity is 0.1-7h
-1; The pH value of reaction system is 5-8.
11. according to the method in claim 1,2 and 8-10 described in any one, and wherein, described alcohol is methyl alcohol.
12. according to the method in claim 1,2 and 8-10 described in any one, and wherein, described alkene is propylene.
13. according to the method in claim 1,2 and 8-10 described in any one, and wherein, described superoxide is hydrogen peroxide.
14. methods according to claim 1, wherein, the aspect ratio of described tubular reactor is 10-200:1.
15. methods according to claim 1 or 14, wherein, the internal diameter of described tubular reactor is 200-2000mm.
16. methods according to claim 1, wherein, the described catalyzer with catalytic hydrogenation comprises carrier and load activeconstituents on the carrier and auxiliary agent, in the total amount of described catalyzer for benchmark and with element, the content of described activeconstituents is 5-20 % by weight, and the content of described auxiliary agent is 0.5-5 % by weight, and the content of described carrier is 75-94.5 % by weight, described activeconstituents is Ni and/or Co, and described auxiliary agent is Ti.
17. methods according to claim 1, wherein, described liquid-phase hydrogenatin treatment condition comprise: temperature is 80-150 DEG C; In gauge pressure, pressure is 1.5-4MPa; Volume space velocity containing hydrogen retrieval alcoholic solvent is 5-15h
-1.
18. methods according to claim 1, wherein, the method also comprises the recovery alcoholic solvent after to hydrogenation and carries out rectifying and collect alcohol cut.
19. 1 kinds of olefin epoxidation process, the method comprises:
(1) under epoxidation reaction of olefines condition, at least one alkene, at least one superoxide are contacted with at least one HTS with at least one alcohol as solvent, obtains the liquid reaction mixture containing epoxide;
(2) described liquid reaction mixture is separated, obtains epoxide and reclaim alcoholic solvent;
(3), after adopting the method in claim 1-8 and 14-18 described in any one to carry out purifying to described recovery alcoholic solvent, be circulated in step (1) as at least part of described solvent.
20. methods according to claim 19, wherein, described epoxidation reaction of olefines condition comprises: the mol ratio of solvent, alkene and hydrogen peroxide is (4-15): (1-5): 1; Temperature is 30-150 DEG C; In gauge pressure, pressure is 0.5-4.5MPa; During liquid, volume space velocity is 0.1-7h
-1; The pH value of reaction system is 5-8.
21. methods according to claim 19 or 20, wherein, described alcohol is methyl alcohol.
22. methods according to claim 19 or 20, wherein, described superoxide is hydrogen peroxide.
23. methods according to claim 19 or 20, wherein, described alkene is propylene.
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| CN113968772A (en) * | 2020-07-24 | 2022-01-25 | 中国石油化工股份有限公司 | Purification method and apparatus, mixed stream processing method and apparatus, method for producing epoxide, and epoxidation reaction system |
| CN113968829A (en) * | 2020-07-24 | 2022-01-25 | 中国石油化工股份有限公司 | Propylene epoxidation method and epoxidation system |
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