CN104926643B - A kind of method producing succinic acid - Google Patents
A kind of method producing succinic acid Download PDFInfo
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- CN104926643B CN104926643B CN201410107832.3A CN201410107832A CN104926643B CN 104926643 B CN104926643 B CN 104926643B CN 201410107832 A CN201410107832 A CN 201410107832A CN 104926643 B CN104926643 B CN 104926643B
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- tubular reactor
- hole
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- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 239000001384 succinic acid Substances 0.000 title claims abstract description 57
- 239000001257 hydrogen Substances 0.000 claims abstract description 89
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 89
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 79
- 239000002994 raw material Substances 0.000 claims abstract description 75
- 239000011148 porous material Substances 0.000 claims abstract description 35
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 26
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims abstract description 16
- FPYJFEHAWHCUMM-UHFFFAOYSA-N Maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 10
- VZCYOOQTPOCHFL-UHFFFAOYSA-N fumaric acid Chemical compound OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011976 maleic acid Substances 0.000 claims abstract description 9
- 239000007789 gas Substances 0.000 claims description 62
- 238000002156 mixing Methods 0.000 claims description 33
- 239000007788 liquid Substances 0.000 claims description 31
- 239000012528 membrane Substances 0.000 claims description 26
- 239000012530 fluid Substances 0.000 claims description 24
- 230000000694 effects Effects 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 239000011344 liquid material Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 23
- 238000000034 method Methods 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 73
- 230000000052 comparative effect Effects 0.000 description 17
- 239000000463 material Substances 0.000 description 14
- 239000000203 mixture Substances 0.000 description 13
- 239000011159 matrix material Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- 239000000969 carrier Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000007792 addition Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229920002961 Polybutylene succinate Polymers 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 244000052616 bacterial pathogens Species 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000005712 crystallization Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000000855 fermentation Methods 0.000 description 2
- 230000004151 fermentation Effects 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 239000004631 polybutylene succinate Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 230000002194 synthesizing Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N TiO Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229920000704 biodegradable plastic Polymers 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000000875 corresponding Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 238000011031 large scale production Methods 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000011068 load Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- -1 poly butylene succinate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 230000003068 static Effects 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910001929 titanium oxide Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Abstract
The invention provides a kind of method producing succinic acid, injected in the solution containing raw material by the hole that average pore size is nano-scale including by hydrogen, obtain containing hydrogen solution, described raw material is maleic anhydride and/or maleic acid；Send into described in the way of flowing up in tubular reactor containing hydrogen solution, make the described hydrogen solution that contains contact with the catalyst with catalytic hydrogenation being seated in described tubular reactor, carry out hydrogenation reaction.Compared with using trickle bed hydrogenation technique, in the case of remaining condition is identical, the method is obtained in that higher feed stock conversion and selectivity of product, it is thus achieved that purity reaches the succinic acid of 99.9%.Further, the method drastically increases the efficiency of hydrogenation reaction, improves effective treating capacity of catalyst, decreases the volume of reactor, reduces investment and production cost.
Description
Technical field
The present invention relates to a kind of method producing succinic acid.
Background technology
Succinic acid popular name succinic acid, is a kind of important fine chemical product and organic synthesis intermediate, extensively
General it is applied in the industry such as synthetic plastic, rubber, medicine, food, coating.In recent years, should due to it
Constantly expanding with field, the demand of this product is increased by domestic and international market the most day by day.Particularly in synthesis
In biodegradable plastic poly butylene succinate (PBS), the demand of succinic acid will rapidly be increased,
Wide market.
The production method of succinic acid is a lot, but the method industrially applied only has microbe fermentation method, electricity
Chemical synthesis and catalytic hydrogenation method.It is loaded down with trivial details that microbe fermentation method prepares succinic acid technique, wastewater discharge
Greatly, separation costs is produced high.Electrochemical synthesis is also referred to as electrolysis, the current efficiency of the method and conversion
Rate is the highest, and power consumption is big, electrolysis bath maintenance difficult, and floor space is big, is unfavorable for large-scale production.
Catalytic hydrogenation method is to make maleic anhydride or maleic acid that hydrogenation reaction to occur under catalyst action,
Generate succinic acid.
CN101844976B discloses a kind of method that fixed bed continuous catalytic hydrogenation prepares succinic acid, should
Method provide a kind of environmental protection can the technique of large-scale continuous production succinic acid, and catalyst is granule
Shape loaded catalyst, it is not necessary to carry out product and separate with catalyst.But the method uses common solid
Fixed bed (i.e. trickle bed) catalytic hydrogenation process.In trickle bed catalytic hydrogenation process, gas-liquid mixing is uneven
Even, the mass transfer effect between airwater mist cooling is poor, and hydrogen is dispersed to the speed on material liquid and catalyst
Relatively slow, catalyst surface utilization rate is low, and material liquid must can be only achieved by stay longer on a catalyst
Preferably being hydrogenated with effect, thus cause hydrogenation reactor volume relatively big, catalyst treatment amount is the highest, increases
Investment and production cost；And channel in beds, wall stream are serious, hydrogenation temperature is difficult to control to,
It is easily formed hot(test)-spot temperature, causes side reaction to increase, thus affect hydrogenation efficiency.
Summary of the invention
It is an object of the invention to the deficiency overcoming existing catalytic hydrogenation succinic acid technique to exist, it is provided that
A kind of method producing succinic acid.
The present inventor finds in research process: be nano-scale by hydrogen by average pore size
Hole is sent in the solution containing maleic anhydride and/or maleic acid, it is possible to preferably dissolved by hydrogen
And be dispersed in this solution；By obtain to send into ratio of height to diameter in the way of flowing up containing hydrogen solution bigger
Carrying out catalytic hydrogenation reaction in tubular fixed-bed reactor, in course of reaction, beds is immersed in hydrogeneous
In solution, dissolve and disperse hydrogen in the solution and maleic anhydride and/or maleic acid and urge
The avtive spot of agent combines and reacts, and so can be effectively improved the efficiency of hydrogenation reaction, reduces
Side reaction, it is thus achieved that higher feed stock conversion and selectivity of product.Complete the present invention on this basis.
The invention provides a kind of method producing succinic acid, the method includes hydrogen is passed through average pore size
Hole for nano-scale is injected in the solution containing raw material, obtains containing hydrogen solution, and described raw material is maleic two
Anhydride and/or maleic acid；By described tubular reactor of sending in the way of flowing up containing hydrogen solution
In, make described containing hydrogen solution and the catalysis with catalytic hydrogenation being seated in described tubular reactor
Agent contacts, and carries out hydrogenation reaction.
The method using the present invention produces succinic acid, compared with using trickle bed hydrogenation technique, at remaining
In the case of part is identical, it is possible to obtain higher feed stock conversion and selectivity of product, it is thus achieved that succinic acid
Purity the highest.Specifically, the purity adopting the succinic acid product being obtained by the present invention can reach
To more than 99.9%, meet pharmaceutical grade and polymer grade prescription.
The method according to the invention, hydrogenation reaction is carried out in the liquid phase, dissolves and is dispersed in containing in hydrogen solution
Hydrogen be enough to provide enough hydrogen source into hydrogenation reaction, drastically increase the efficiency of hydrogenation reaction, carry
High effective treating capacity of catalyst, decreases the volume of reactor, reduces investment and production cost；
Simultaneously, moreover it is possible to avoid present in trickle bed technique channel in beds, wall stream serious, hydrogenation temperature
Spend unmanageable deficiency.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and constitutes the part of description, with
Detailed description below is used for explaining the present invention together, but is not intended that limitation of the present invention.?
In accompanying drawing:
Fig. 1 adjacent fluid passage in the Liqiud-gas mixing device that schematically the explanation present invention uses is gentle
A kind of preferred implementation of the component of body passage.
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 Liqiud-gas mixing device that the present invention uses.
A kind of embodiment of the method that Fig. 5 provides for the present invention.
The another embodiment of the method that Fig. 6 provides for the present invention.
Another embodiment of the method that Fig. 7 provides for the present invention.
Fig. 8 is for illustrating the annexation between Liqiud-gas mixing device and tubular reactor.
Description of reference numerals
1: passage 2: tube wall
3: perforated membrane 4: for adjoining the component of fluid passage and gas passage
5: housing 6: gas access
7: liquid inlet 8: liquid outlet
9: Liqiud-gas mixing device 10: hydrogen
11: the solution 12 containing raw material: tubular reactor
13: ring flange 14: ring flange
15: ring flange 16: ring flange
Detailed description of the invention
The invention provides a kind of method producing succinic acid, the method includes hydrogen is passed through average pore size
Hole for nano-scale is injected in the solution containing raw material, obtains containing hydrogen solution, and described raw material is maleic two
Anhydride and/or maleic acid；By described send in the way of flowing up containing hydrogen solution tubular fixed-bed instead
Answer in device, make the described hydrogen solution that contains contact with the catalyst with catalytic hydrogenation, carry out hydrogenation reaction.
In the present invention, described average pore size be the average pore size in the hole of nano-scale can be typically 1nm extremely
1000nm, preferably 30nm to 1000nm, more preferably 30nm to 500nm.Described average hole
Footpath uses scanning electron microscope method to measure.
Various method can be used to be injected containing raw material by the hole that average pore size is nano-scale by hydrogen
In solution.
In the preferred embodiment of the present invention, hydrogen is injected into by a kind of Liqiud-gas mixing device and contains
In the solution of raw material, described Liqiud-gas mixing device includes that at least one is for the liquid accommodating the solution containing raw material
Body passage and at least one gas passage being used for accommodating hydrogen, described fluid passage and described gas passage
Between adjoined by a component, described component at least partially have porose area, described in have porose area to have described
Average pore size is the hole of nano-scale, and hydrogen is injected into by the hole that described average pore size is nano-scale and contains
In the solution of raw material.In the present invention, term " fluid passage " refers to the receiving solution containing raw material
Space；Term " gas passage " refers to accommodate the space of hydrogen.
Described component at least partially have porose area, described in have porose area to prolong along the length direction of described component
Stretch.Preferably, porose area is had to cover whole component (that is, described fluid passage and described gas passage described in
Between by have the hole that described average pore size is nano-scale component adjoin, hydrogen is by described hole
It is injected in the solution containing raw material).Described have porose area to have hole that described average pore size is nano-scale,
So that hydrogen pass through described in there is the hole that average pore size is nano-scale be injected in the solution containing raw material.
Described component can be that the various hydrogen that can make to be contained in described gas passage is by described flat
Equal aperture is that the hole of nano-scale enters the component in the solution containing raw material being contained in fluid passage.
In an example, described component is formed by porous material, and the average pore size in hole therein is nano-scale.
In another example, described component includes matrix and attachment perforated membrane on the matrix, described
Matrix has through hole, described perforated membrane may be located at described matrix be contained in described fluid passage
On the surface of the solution contact containing raw material, it is also possible to be positioned at described matrix be contained in described gas passage
On the surface of interior hydrogen contact.Preferably, described perforated membrane be positioned at described matrix be contained in described
On the surface of the contact of the solution containing raw material in fluid passage.Hole in described perforated membrane is previously described
Average pore size is the hole of nano-scale.The average pore size of the through hole on described matrix is not particularly limited, only
Want to pass through gas.Preferably, the average pore size of the through hole on described matrix be 1nm extremely
1000 μm (such as 50-200 μm).
The shape of described component can select according to the position relationship of fluid passage and gas passage, with
Enable to described fluid passage and described gas passage be as the criterion by this component is adjacent.
In one embodiment of the invention, described component is the pipeline with at least one passage.Institute
State and there is on the tube wall of pipeline through hole, and the average 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,
Being attached with perforated membrane on the outer wall of described pipeline and/or the inwall of passage, described tube wall has through hole, described
Hole on perforated membrane be average pore size be the hole of nano-scale, below this component is referred to as membrane tube.Specifically
Ground, as Figure 1-3, described component is the membrane tube with at least one passage.Described membrane tube is with tube wall
Having the pipeline of through hole on 2 as matrix, described pipeline has at least one passage 1, described pipeline
It is attached with perforated membrane 3 on the inwall of passage 1 and/or the outer wall of pipeline.The average pore size of the through hole on tube wall
Be not particularly limited, as long as hydrogen can be made to pass through, can be typically 1nm to 1000 μm (as
50-200 μm)；Hole on described perforated membrane be previously described average pore size be the hole of nano-scale.
In above two embodiment, the quantity of the passage on described pipeline or described membrane tube is preferably extremely
Few two, such as 4-20 bar.
In actual mechanical process, when described component is pipeline or membrane tube, as shown in Figure 4, described gas
Liquid mixing arrangement can also include housing 5, is placed in housing 5 by least one component 4, and makes component
Existential Space between outer wall and the inwall of housing 5 of 4.Passage on described component contains as receiving
The space that the inwall of the described fluid passage of the solution of raw material, the outer wall of described component and described housing is formed
As the described gas passage for accommodating hydrogen；Or, the passage on described component is as being used for accommodating
The described gas passage of hydrogen, the space that the inwall of the outer wall of described component and described housing is formed as with
Described fluid passage in the solution accommodated containing raw material.Preferably, the passage on described component is as being used for
Accommodating the described fluid passage of the solution containing raw material, the outer wall of described component is formed with the inwall of described housing
Space as accommodating the described gas passage of hydrogen.
As shown in Figure 4, housing 5 has gas access 6, liquid inlet 7 and liquid outlet 8, gas
Passage connects with gas access 6, and the two ends of fluid passage connect with liquid inlet 7 and liquid outlet 8 respectively
Logical.Hydrogen is sent in gas passage by gas access 6, the solution containing raw material is sent into fluid passage
In, under the effect of pressure differential, the hole making hydrogen pass through on tube wall enters in the described solution containing raw material,
Thus obtain containing hydrogen solution.
The material forming described component can be inorganic material (such as inorganic ceramic), it is also possible to for organic material
Material, as long as the material forming this component with hydrogen and the solution generation chemical interaction containing raw material is not
Can.
Described component filling rate in described housing can be typically 20-50%.Described filling rate refers to
The percent value of the total measurement (volume) of the space that component occupies and housing.
The amount sending into the hydrogen in the solution containing raw material can select according to concrete reaction condition.This
Hydrogen is sent in the solution containing raw material by the hole that average pore size is nano-scale by the method for invention, it is possible to
Make hydrogen high degree of dispersion and be dissolved in the solution containing raw material, thus providing enough hydrogen for hydrogenation reaction
Source.Therefore, even if the method for the present invention does not send into hydrogen in the solution containing raw material in a large number, simultaneously without
Maintain certain hydrogen dividing potential drop in the reactor, also can obtain good hydrotreating effect, and reduce catalysis
The trend of agent coking.According to the inventive method, described hydrogen can once or by several times be sent into and contain the molten of raw material
In liquid, it can be 1-2:1 that feeding amount and this of hydrogen contains the mol ratio of the raw material in the solution of raw material, excellent
Elect 1-1.5:1 as.
It is in hydrogenation temperature with the method for the invention it is preferred to hydrogen to be sent into temperature and pressure and adds hydrogen pressure
In the solution containing raw material under power, so can reduce hydrogen further from containing becoming of escaping hydrogen solution
Gesture.Specifically, hydrogen can be sent into temperature and be 60-120 DEG C and pressure is that 0.5-2MPa(is with gauge pressure
Meter) the solution containing raw material in.
Described tubular reactor refers to the reactor with relatively larger ratio of height to diameter.Specifically, described pipe reaction
The height of device can be 10-200:1(such as 10-50:1 with the ratio (that is, ratio of height to diameter) of internal diameter).Institute
The internal diameter stating tubular reactor can be conventional selection, such as, can be 20-2000mm.With still reaction
Device is compared, and uses tubular reactor on the one hand can reduce the volume of reactor, on the other hand by front
During Liqiud-gas mixing device described in literary composition (particularly be pipeline or membrane tube at described component), directly by described
Liqiud-gas mixing device is arranged on the material inlet pipeline of described tubular reactor, flexible operation and side
Just.
The method according to the invention, described be admitted to described tubular type in the way of flowing up containing hydrogen solution anti-
Answer in device.And can be seated in by sending into described from the bottom of described tubular reactor containing hydrogen solution
The catalyst contact with catalytic hydrogenation in the beds of described tubular reactor, and will connect
After touching the hydrogenation obtained, logistics exports from the top of described tubular reactor.
The method according to the invention, the quantity of described tubular reactor can be 1, it is also possible to is 2
Above.When the quantity of described tubular reactor is more than 2, described tubular reactor can be series connection
Connect, it is also possible to for being connected in parallel, it is also possible to for series connection and combination in parallel.Described being connected in series refers to
The effluent of previous tubular reactor is the charging of next tubular reactor；Described being connected in parallel refers to
Material is not had to exchange between tubular reactor.
In the described solution containing raw material, the concentration of raw material can be conventional selection.Usually, described containing raw material
Solution in the concentration of raw material be 10-40 weight %.It is be connected in series at tubular fixed-bed reactor
During two or more tubular fixed-bed reactor, the concentration of raw material refers to enter first tubular fixed-bed reaction
The concentration of the raw material in the solution containing raw material of device.
The present invention is not particularly limited for the solvent of the described solution containing raw material, can be various can be molten
Solve raw material and the liquid substance of succinic acid.Preferably, the solvent of the described solution containing raw material is water, so
Not only environmental protection, and can the operating cost of the method for the present invention further.
Described can enter under conventional hydroprocessing temperature and pressure containing contacting of hydrogen solution and catalyst
OK, it is not particularly limited.Usually, make described containing hydrogen solution and the catalyst with catalytic hydrogenation
The condition of contact includes: temperature can be 60-120 DEG C；In terms of gauge pressure, in tubular fixed-bed reactor
Pressure can be 0.5-2MPa；The weight (hourly) space velocity (WHSV) of liquid material can be 2-10h-1。
Use previously described Liqiud-gas mixing device that hydrogen is injected the solution containing raw material, hydrogeneous molten to obtain
Liquid, and hydrogen solution will be contained when sending into tubular reactor, described Liqiud-gas mixing device is used for export hydrogeneous molten
The internal diameter of the outlet of liquid is r1, the internal diameter of the entrance that described tubular reactor contains hydrogen solution for input is
r2, r1/r2=0.6-1(such as 0.85-1).The internal diameter of the pipe connecting described outlet and described entrance is r3,
r1/r3=0.85-1.5(such as 0.85-1).It is so more stable in transport process containing hydrogen solution such that it is able to
Obtain and be preferably hydrogenated with effect.
Shown in Fig. 5 be the one of the method according to the invention preferred embodiment.In this embodiment,
Hydrogen 10 is injected in the solution 11 containing raw material by Liqiud-gas mixing device 9, obtains containing hydrogen solution.Contain
Hydrogen solution enters in tubular reactor 12 and contacts with catalyst, thus carries out hydrogenation reaction, is contained
The reactant mixture of succinic acid.
According to this embodiment, multiple tubular reactor (such as two or more tubular reactor) can be set,
Can be to be connected in series between multiple tubular reactors, it is also possible to for being connected in parallel, it is also possible to for series connection with
Combination in parallel.When multiple tubular reactors are connected in series, along the flow direction of material, can be by gas
Liquid mixing arrangement is arranged on the arrival end of first tubular reactor；Can also as shown in Figure 6, each
The arrival end of tubular reactor 12 is respectively provided with Liqiud-gas mixing device 9.In multiple tubular reactor parallel connections even
When connecing, a Liqiud-gas mixing device can be only set, the solution containing raw material is mixed with hydrogen, then will
Obtain is respectively fed in the multiple tubular reactors being connected in parallel containing hydrogen solution；Can also be as shown in Figure 7
Arrival end at each tubular reactor 12 is respectively provided with Liqiud-gas mixing device 9.
Can adopt and in various manners Liqiud-gas mixing device is connected on entrance pipe, such as: can be at gas
The two ends of liquid mixing arrangement respectively arrange a ring flange (Fig. 8 is shown in which a ring flange 13), respectively
(as shown in Figure 8, Liqiud-gas mixing device one end is connected from the flangeseal on corresponding entrance pipe
Ring flange 13 be tightly connected with the ring flange 14 on entrance pipe)；The other end of entrance pipe passes through
Ring flange 15 is connected with the ring flange 16 of the arrival end of tubular reactor 12.
The method of the present invention is not particularly limited for the kind with the catalyst of catalytic hydrogenation, can
Think the material of the common various hydrogenation reactions that can be catalyzed maleic anhydride and/or maleic acid.
Preferably, described catalyst includes carrier and load active component on the carrier, described activity
Composition is preferably one or more in Pd, Pt, Ru, Rh and Ir.In described catalyst, live
The content of property composition can be 0.1-2 weight %.The carrier of described loaded catalyst can be conventional choosing
Select, be not particularly limited.Usually, described carrier can be in silicon oxide, activated carbon and titanium oxide
One or more.
The method according to the invention, when described raw material contains maleic anhydride, if containing the molten of raw material
The solvent of liquid is water, and maleic anhydride occurs hydrolysis during hydrogenation reaction simultaneously, is formed
Succinic acid.When solvent at the described solution containing raw material is nonaqueous solvent (that is, water-free solvent),
The method also includes that the reactant mixture obtained by hydrogenation is hydrolyzed, to obtain succinic acid.Described hydrolysis
Can carry out under normal conditions.Usually, water and maleic anhydride in the described solution containing raw material
Mol ratio can be 1-1.5:1.Hydrolysis temperature can be 5-50 DEG C.
The method according to the invention, it is also possible to include dividing the effluent from tubular reactor or hydrolyzate
Separate out succinic acid.Can use conventional various methods from the effluent or hydrolyzate of tubular reactor
Isolate succinic acid.Such as: effluent or hydrolyzate can be cooled down, make succinic acid crystallization,
And carry out solid-liquid separation, thus obtain as solid succinic acid product.Surplus solution is purified or the most purified
Can recycle.The method feed stock conversion of the present invention is high, has isolated the surplus solution of succinic acid i.e.
Make not to be purified direct reuse, also can prepare the succinic acid that purity is 99.9%.
Below in conjunction with embodiment and comparative example, the present invention is described in detail, but and is not so limited this
The scope of invention.
In following example and comparative example, using scanning electron microscope method to measure average pore size, pressure is all with table
Pressure meter.
In following example and comparative example, use high performance liquid chromatography to the effluent of hydrogenation reactor
Composition is analyzed, and on this basis, uses below equation to calculate feed stock conversion and succinic acid selectivity.
Feed stock conversion=[addition of (weight of raw material in the addition weight-effluent of raw material)/raw material
Weight] × 100%；
Succinic acid selectivity=[molal quantity of succinic acid in reactant mixture/(the addition mole of raw material-
The mole of raw material in effluent)] × 100%.
In following example and comparative example, use the purity of high effective liquid chromatography for measuring succinic acid product.
Embodiment 1-8 is for the method that the present invention is described.
Embodiment 1
The method shown in Fig. 6 of employing, by the solution (the maleic anhydride aqueous solution of 25wt%) containing raw material
Mix under conditions of table 1 is listed in first Liqiud-gas mixing device with hydrogen, then will obtain
Containing hydrogen solution send into first tubular reactor (internal diameter of tubular reactor is 50mm, pipe reaction
Being provided with 1 beds in device, the ratio of height to diameter of Catalyst packing is 15:1) in, in table 1 institute
Under conditions of showing, (active component is with the catalyst with catalytic hydrogenation
0.5wt%Pd+1.5wt%Ru, carrier is activated carbon) contact.
Under conditions of table 1 is listed, by second Liqiud-gas mixing device to first tubular reactor
Effluent injects after hydrogen, sends into second tubular reactor containing hydrogen mixture by obtain (tubular type is anti-
The internal diameter answering device is 50mm, is provided with 1 beds in tubular reactor, Catalyst packing
Ratio of height to diameter is 10:1) in, (urge with the catalyst with catalytic hydrogenation under the conditions shown in Table 1
Agent is identical with first tubular reactor) contact.
By the effluent crystallisation by cooling of second tubular reactor, then carry out solid-liquid separation, obtain solid
Succinic acid and reaction raffinate, obtain succinic acid product after drying by the solid obtained washing, and its purity exists
Table 1 is listed.Use high performance liquid chromatography that the composition of the effluent of second tubular reactor is carried out
Analyzing, and calculate feed stock conversion and succinic acid selectivity, result is listed in Table 1.
Wherein, Liqiud-gas mixing device is used for the component of abutting gas passage and fluid passage for such as Fig. 2 institute
The membrane tube shown (commercially available from BeiJing ZhongTianYuan Environment Engineering Co., Ltd, pipeline is evenly distributed with 19
Individual fluid passage, the internal diameter of each fluid passage is 3.3mm, and the average pore size in the hole on matrix is
100 μm, the average pore size in the hole on perforated membrane is 30nm) and with this membrane tube with the use of a shell
Body, the outer wall of membrane tube is gas passage with the space of the inwall formation of housing, membrane tube filling in the housing
Rate is 40%.
The ratio of the internal diameter of the material outlet of Liqiud-gas mixing device and the internal diameter of the material inlet of tubular reactor
Value is 0.9, the internal diameter of the material outlet of Liqiud-gas mixing device and the material outlet being connected Liqiud-gas mixing device
It is 0.9 with the ratio of the internal diameter of the pipeline of the material inlet of tubular reactor.
Comparative example 1
Use method same as in Example 1 to produce succinic acid, except for the difference that, Liqiud-gas mixing device is used
In the membrane tube of abutting gas passage and fluid passage, the average pore size on perforated membrane is 5 μm, at aperture
The ratio accounting for total hole in the hole in 5-5.5 μ m be 95%(commercially available from Beijing in Tianyuan environmental project
Co., Ltd).
Experimental result is listed in Table 1.
Comparative example 2
Using method same as in Example 1 to produce succinic acid, except for the difference that, Liqiud-gas mixing device is with quiet
State blender (purchased from the SV type static mixer of the suitable many petrochemical equipments company limited of Qidong person of outstanding talent) replaces.
Experimental result is listed in Table 1.
Comparative example 3
Using method same as in Example 1 to produce succinic acid, except for the difference that, liquid material is anti-in tubular type
Answer the flow direction in device for flowing downward.
Experimental result is listed in Table 1.
Table 1
*: the mol ratio of raw material in the solution that hydrogen and hydrogen are sent into
Embodiment 2
Method same as in Example 1 is used to produce succinic acid, except for the difference that, used by Liqiud-gas mixing device
The average pore size in the hole on the perforated membrane of membrane tube is 500nm.
Experimental result is listed in table 2.
Embodiment 3
Method same as in Example 1 is used to produce succinic acid, except for the difference that, in the solution containing raw material
Raw material is maleic acid, and the component being used for adjoining fluid passage and gas passage in Liqiud-gas mixing device is
The pipeline formed by porous material is (commercially available from BeiJing ZhongTianYuan Environment Engineering Co., Ltd；On pipeline
Being evenly distributed with 19 passages, the internal diameter of each passage is 3.3mm, the average pore size in the hole on tube wall
For 250nm)；Using the passage on pipeline as fluid passage, by the inwall shape of the outer wall of pipeline Yu housing
The space become is as gas passage, and pipeline filling rate in the housing is 45%.
Experimental result is listed in table 2.
Table 2
| Project | Embodiment 2 | Embodiment 3 |
| Feed stock conversion/% | 99.7 | 99.5 |
| Succinic acid selectivity/% | 100 | 100 |
| Succinic acid purity/% | 99.9 | 99.9 |
Embodiment 4-7
Method same as in Example 1 is used to produce succinic acid, except for the difference that, in the condition that table 3 is listed
Lower hydrogen is mixed with the solution containing raw material, and under conditions of table 3 is listed, carry out hydrogenation reaction.
Experimental result is listed in table 3.
Table 3
*: the mol ratio of raw material in the solution that hydrogen and hydrogen are sent into
Embodiment 1-7 as a result, it was confirmed that use the present invention method prepare succinic acid, it is possible to obtain high
Feed stock conversion and succinic acid selectivity, and the purity of the succinic acid prepared is high, it is possible to reach 99.9%.
Embodiment 8
The present embodiment uses the reaction raffinate having isolated succinic acid in embodiment 1 to prepare containing raw material
Solution, and under the same conditions as example 1 hydrogen is mixed and fed into tubular type with the solution containing raw material
Reactor carries out hydrogenation reaction.
Experimental result is listed in table 4.
Comparative example 4
This comparative example uses the reaction raffinate preparation having isolated succinic acid in comparative example 1 to contain the molten of raw material
Liquid, and it is anti-under conditions of identical with comparative example 1, hydrogen and the solution containing raw material to be mixed and fed into tubular type
Answer and device carries out hydrogenation reaction.
Experimental result is listed in table 4.
Comparative example 5
This comparative example uses the reaction raffinate preparation having isolated succinic acid in comparative example 2 to contain the molten of raw material
Liquid, and it is anti-under conditions of identical with comparative example 2, hydrogen and the solution containing raw material to be mixed and fed into tubular type
Answer and device carries out hydrogenation reaction.
Experimental result is listed in table 4.
Table 4
| Project | Embodiment 8 | Comparative example 4 | Comparative example 5 |
| Feed stock conversion/% | 99.9 | 91.8 | 85.1 |
| Succinic acid selectivity/% | 100 | 98.2 | 97.0 |
| Succinic acid purity/% | 99.9 | 97.1 | 94.6 |
Embodiment 8 as a result, it was confirmed that the method for the present invention i.e. use isolated succinic acid reaction residue
The liquid preparation solution containing raw material, also can prepare the succinic acid that purity is 99.9%, on the one hand the explanation present invention
The feed stock conversion of method high, the by-product in the reactant mixture obtained is few；On the other hand also illustrate
When the method for the present invention is to produce on a large scale, it is possible to realize recycling of waste liquid, greatly reduce
The waste liquid amount produced.
Claims (13)
1. the method producing succinic acid, it is nanometer chi that the method includes hydrogen by average pore size
Very little hole is injected in the solution containing raw material, obtains containing hydrogen solution, described raw material be maleic anhydride and/
Or maleic acid；Send into described in the way of flowing up in tubular reactor containing hydrogen solution, make institute
State and contact with the catalyst with catalytic hydrogenation being seated in described tubular reactor containing hydrogen solution,
Carry out hydrogenation reaction, wherein, hydrogen is injected the described solution containing raw material by a kind of Liqiud-gas mixing device
In, thus obtaining described containing hydrogen solution, described Liqiud-gas mixing device includes that at least one is described for accommodating
The fluid passage of the solution containing raw material and at least one gas passage being used for accommodating described hydrogen, described liquid
Adjoined by a component between body passage and described gas passage, described component the most porose
District, described in have porose area to have hole that described average pore size is nano-scale, described hydrogen by described averagely
Aperture is that the hole of nano-scale is injected in the described solution containing raw material.
Method the most according to claim 1, wherein, described component is for having at least one passage
Pipeline, the tube wall of described pipeline has through hole, the average pore size of described through hole is nano-scale；Or
It is attached with perforated membrane on the outer wall of pipeline described in person and/or the inwall of passage, the tube wall of described pipeline has
Through hole, the hole on described perforated membrane be average pore size be the hole of nano-scale.
Method the most according to claim 2, wherein, described Liqiud-gas mixing device also includes housing,
Being placed in described housing by least one component, described housing has gas access, liquid inlet and liquid
Outlet, Existential Space between outer wall and the inwall of described housing of described component, the outer wall of described pipeline with
The space that the inwall of described housing is formed is as described gas passage, and the passage on described pipeline is as described
Fluid passage, described gas passage connects with described gas access, the two ends of described fluid passage respectively with
Described liquid inlet connects with described liquid outlet.
4. according to the method described in any one in claim 1-3, wherein, described gas-liquid mixed dress
Put the arrival end being arranged on described tubular reactor.
5. according to the method described in any one in claim 1-3, wherein, average pore size is nanometer
The average pore size in the hole of size is 1-1000nm.
6. according to the method described in any one in claim 1-3, wherein, hydrogen is sent into temperature
For in 60-120 DEG C and the solution containing raw material that pressure is 0.5-2MPa.
7. according to the method described in any one in claim 1-3, wherein, the feeding amount of hydrogen with
The mol ratio of the raw material in the described solution containing raw material is 1-2:1.
Method the most according to claim 1, wherein, the solvent of the described solution containing raw material is water.
Method the most according to claim 1, wherein, the ratio of height to diameter of described tubular reactor is
10-200:1.
10. according to the method described in claim 1 or 9, wherein, the internal diameter of described tubular reactor is
20-2000mm。
11. according to the method described in any one in claim 1-3 and 9, and wherein, described tubular type is anti-
Answering the two or more tubular reactor that device includes being connected in series, the arrival end at each tubular reactor is arranged
Hydrogen inlet.
12. methods according to claim 1, wherein, make the described hydrogen solution that contains add with having catalysis
The condition of the catalyst contact of hydrogen effect includes: temperature is 60-120 DEG C；In terms of gauge pressure, tubular reactor
Interior pressure is 0.5-2MPa；The weight (hourly) space velocity (WHSV) of liquid material is 2-10h-1。
13. methods according to claim 8, wherein, the method also includes from tubular reactor
Effluent is isolated succinic acid, and by remaining solution direct reuse.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410107832.3A CN104926643B (en) | 2014-03-21 | A kind of method producing succinic acid |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410107832.3A CN104926643B (en) | 2014-03-21 | A kind of method producing succinic acid |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101890323A (en) * | 2009-05-22 | 2010-11-24 | 山西侨友化工股份有限公司 | Reactor for preparing succinyl oxide by maleic anhydride hydrogenation |
| JP2013023464A (en) * | 2011-07-20 | 2013-02-04 | Kawasaki Kasei Chem Ltd | Method for producing succinic acid |
| CN103570650A (en) * | 2013-11-13 | 2014-02-12 | 山西大学 | Technological process for continuously producing succinic anhydride and co-producing succinic acid through maleic anhydride hydrogenation |
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101890323A (en) * | 2009-05-22 | 2010-11-24 | 山西侨友化工股份有限公司 | Reactor for preparing succinyl oxide by maleic anhydride hydrogenation |
| JP2013023464A (en) * | 2011-07-20 | 2013-02-04 | Kawasaki Kasei Chem Ltd | Method for producing succinic acid |
| CN103570650A (en) * | 2013-11-13 | 2014-02-12 | 山西大学 | Technological process for continuously producing succinic anhydride and co-producing succinic acid through maleic anhydride hydrogenation |
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