CN106146345A - Method for producing adiponitrile by adipic acid liquid phase method - Google Patents
Method for producing adiponitrile by adipic acid liquid phase method Download PDFInfo
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- CN106146345A CN106146345A CN201510185122.7A CN201510185122A CN106146345A CN 106146345 A CN106146345 A CN 106146345A CN 201510185122 A CN201510185122 A CN 201510185122A CN 106146345 A CN106146345 A CN 106146345A
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- Prior art keywords
- adipic acid
- adiponitrile
- liquid phase
- phosphoric acid
- phase method
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- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 title claims abstract description 131
- 238000000034 method Methods 0.000 title claims abstract description 83
- 239000001361 adipic acid Substances 0.000 title claims abstract description 65
- 235000011037 adipic acid Nutrition 0.000 title claims abstract description 65
- 239000007791 liquid phase Substances 0.000 title claims abstract description 40
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000004519 manufacturing process Methods 0.000 title abstract description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 162
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 81
- 239000003054 catalyst Substances 0.000 claims abstract description 48
- 239000007787 solid Substances 0.000 claims abstract description 45
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000003085 diluting agent Substances 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 60
- 239000000243 solution Substances 0.000 claims description 29
- 229910021529 ammonia Inorganic materials 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 14
- 230000004044 response Effects 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 9
- 239000008187 granular material Substances 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- 238000000748 compression moulding Methods 0.000 claims description 3
- 239000004744 fabric Substances 0.000 claims description 3
- ZTOMUSMDRMJOTH-UHFFFAOYSA-N glutaronitrile Chemical compound N#CCCCC#N ZTOMUSMDRMJOTH-UHFFFAOYSA-N 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 230000007547 defect Effects 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- 230000009286 beneficial effect Effects 0.000 description 16
- 230000018044 dehydration Effects 0.000 description 16
- 238000006297 dehydration reaction Methods 0.000 description 16
- 230000008569 process Effects 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- 238000005245 sintering Methods 0.000 description 8
- 239000000376 reactant Substances 0.000 description 7
- 229910019142 PO4 Inorganic materials 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000007598 dipping method Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000010452 phosphate Substances 0.000 description 5
- -1 phosphate ester Chemical class 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229920000137 polyphosphoric acid Polymers 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 239000012808 vapor phase Substances 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
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- Catalysts (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A process for preparing adiponitrile by liquid-phase method with adipic acid includes such steps as adding solid phosphoric acid catalyst, adding adipic acid and diluent, heating while stirring, introducing ammonia gas, and reacting. The invention develops a novel green synthesis method for adiponitrile production, and the solid phosphoric acid catalyst is used, so that various defects brought by the traditional catalyst are avoided, and the catalytic effect is improved.
Description
Technical field
The present invention relates to a kind of adipic acid liquid phase ammoniation process and produce the technology of adiponitrile, production uses a kind of green
Color solid phosphoric acid catalyst.
Background technology
Adiponitrile is the important source material of nylon66 fiber, has the substantial amounts of market demand at home.Wherein, adipic acid
Catalytic ammoniation method is an essential industry metallization processes during adiponitrile produces.Adipic acid catalytic ammoniation method be oneself two
Acid and ammonia react the thick adiponitrile of generation, the technique obtaining finished product after rectification under the effect of dehydration catalyst.Root
According to the difference of adipic acid physical state, this technique is divided into again adipic acid liquid phase method and adipic acid vapor phase method.Wherein,
The reaction temperature of liquid phase method is typically at about 280 DEG C, and vapor phase method is 350 DEG C-420 DEG C.It is different from vapor phase method,
In order to reduce the generation of by-product and tar in liquid phase method, also additionally to add diluent and maintain reaction system temperature
The uniformity of degree.Additionally, liquid phase method is relatively simple due to technological process, ring-type impurity is less, and energy consumption is low,
More by industrial favor.But due to adipic acid selling at exorbitant prices, do not possess cost advantage, in last century 90
Age is gradually eliminated by industrial quarters.But, along with the falling of adipic acid price, following adipic acid liquid phase method is again
Possess the possibility restarted, caused again the attention of people about the green high-efficient catalyst research of this technique.
The reaction of adipic acid liquid phase method is roughly divided into neutralization reaction and dehydration two step, as follows:
HOOC(CH2)4COOH+2NH3→H4NOC(CH2)4CONH4
H4NOC(CH2)4CONH4→NC(CH2)4CN+4H2O
Wherein dehydration is a process being progressively dehydrated, and has a lot of intermediate product and generates.Concrete is anti-
Answer process complex and academia is the most disputable, be the most no longer discussed in detail.
Catalyst conventional in adipic acid liquid phase method is the liquid catalyst such as phosphoric acid, phosphate ester.But this kind of urge
Agent has many disadvantages.First, substantial amounts of phosphoric acid, phosphate ester can produce certain corrosion to reactor and make
With, have influence on normal production.Secondly, this kind of liquid catalyst is soluble in reaction system, along with entering of reaction
OK, easily run off, production needs supplement continuously, add production cost.Additionally, according to
U.S.Pat.5, described in 202,455, in the reaction, phosphoric acid and phosphate ester all can generate polyphosphoric acid, are deposited on anti-
Answer on device wall, affect the heat transfer of external heat source.In order to solve the problem of heat transfer, DE734,558 at phosphoric acid
In be mixed into a certain amount of adsorbent.Adsorbent can from kieselguhr, silicon dioxide, Alumina, clay, point
Son sieve arbitrarily selects.After the addition, polyphosphoric acid is no longer had to be deposited in wall of reactor.But due to not
The reason known, so far there are no all industrial application of this catalyst.Simultaneously as adipic acid liquid phase method is upper
The nineties in century is the most progressively eliminated by industrial quarters, and the research about its catalyst has been at dead state,
Rarely seen in research report.
Compared to liquid catalysts such as traditional phosphoric acid, phosphate esters, solid phosphoric acid catalyst has similar urging
Changing effect, it can also overcome the various disadvantages of liquid catalyst in addition.In reaction, solid phosphoric acid catalyst can delay
On The Drug Release phosphoric acid, phosphoric acid concentration in system is low, and the corrosion to reactor is less.Polyphosphoric acid generates simultaneously
Measuring less, heat transfer can also preferably be carried out.After reaction terminates, by catalyst filtration out, after fired
Also can be used for multiple times.It should be noted that solid phosphoric acid catalyst is the most only in adipic acid gas-phase process
Apply, be not yet present in adipic acid liquid phase method.
Summary of the invention
It is an object of the invention to provide a kind of adipic acid liquid phase method and produce adiponitrile technology one novel green
Production technology, it is to avoid the disadvantage such as polymerization that traditional liquid phosphoric acid catalyst brings, coking, improves product simultaneously
Product productivity, and because of the recyclable recycling of catalyst, better economy.
The present invention provides a kind of method that adipic acid liquid phase method produces adiponitrile, and catalyst is solid phosphoric acid catalysis
Agent, puts into adipic acid and diluent in reactor, heats and stir raw material, reach uniform temperature during reaction
After be passed through ammonia, through after a while reaction after generate product.
Adipic acid liquid phase method of the present invention produces the method for adiponitrile, these, it is preferred to described solid
Phosphoric acid catalyst preparation method is: after a certain amount of kieselguhr is dried 1-2h under the baking oven of 100-140 DEG C,
Dry kieselguhr be impregnated in phosphoric acid solution and the aluminum sulfate solution of 15-25wt% of the 55%-95% of excess
In mixed solution, stir 6-12h, then stand 6-12h；After standing, mixed solution is centrifuged, obtains
Precipitate is dried 6-12 hour in 100-140 DEG C of baking oven；After drying precipitate is placed on pipe type calciner
In, N2At 300 DEG C-700 DEG C roasting 1-2h under protective condition；By its compression molding after cooling, sieve through screen cloth
Obtain the granule of 10-50 mesh after choosing, form solid phosphoric acid catalyst.
Adipic acid liquid phase method of the present invention produces the method for adiponitrile, and wherein, diluent is preferably oneself two
One or more in nitrile, glutaronitrile and pimelic dinitrile, diluent is more preferably adiponitrile.
Adipic acid liquid phase method of the present invention produces the method for adiponitrile, wherein, phosphoric acid solution and diatom
The mass ratio of soil is 10-15, and the addition of sulfate is the 10%-15% of kieselguhr quality.
Adipic acid liquid phase method of the present invention produces the method for adiponitrile, wherein, adipic acid and diluent
Mass ratio is preferably 1:2.
Adipic acid liquid phase method of the present invention produces the method for adiponitrile, and wherein, solid phosphoric acid consumption is preferred
For adipic acid and the 1%-2.5% of diluent gross mass.
Adipic acid liquid phase method of the present invention produces the method for adiponitrile, and wherein, during reaction, speed of agitator is excellent
Elect 1000-2000r/min as.
Adipic acid liquid phase method of the present invention produces the method for adiponitrile, and wherein, during reaction, heating-up temperature is excellent
Elect 260 DEG C-280 DEG C as.
Adipic acid liquid phase method of the present invention produces the method for adiponitrile, wherein, the ammonia being passed through during reaction
Flow is preferably 150L/h-400L/h.
Adipic acid liquid phase method of the present invention produces the method for adiponitrile, and wherein, the response time is preferably
0.5-2h。
The effect of the present invention:
The present invention is during the application of solid phosphoric acid catalyst, and the water that dehydration generates can be by ammonia from reaction
Condenser system brought into by still, and then is collected.Owing in appraisement system, ammonia flow is the most excessive, even if
Do not add catalyst, neutralize the speed of reaction the most quickly, when proceeding to 60min, neutralize reaction fundamental reaction
Completely.Now, dehydrating amount the biggest expression dehydration is the most complete, and the productivity of adiponitrile is the highest.Therefore, choosing
Take the size of dehydration rate (actual dehydrating amount and the ratio of theoretical dehydrating amount) of 60min to characterize catalyst
Catalytic effect.
Experiment finds, when not adding catalyst, dehydration rate only has 18%-41%；Adding traditional liquid
After phosphoric acid catalyst, dehydration rate rises to 46%-85%；When adding solid phosphoric acid, dehydration rate reaches
57%-95%.
Detailed description of the invention
Hereinafter embodiments of the invention are elaborated: the present embodiment is premised on technical solution of the present invention
Under implement, give detailed embodiment and process, but protection scope of the present invention be not limited to following
Embodiment, the experimental technique of unreceipted actual conditions in the following example, generally according to normal condition.
Diatomite support drying condition
In the present invention, kieselguhr drying condition is not particularly limited, generally a certain amount of kieselguhr is existed
100-140 DEG C of dry 1-2h, preferably carrier are at 120 DEG C of dry 2h；
If baking temperature is less than 100 DEG C, owing to baking temperature is too low, cause dry insufficient, or extend
Drying time；And baking temperature is more than 140 DEG C, owing to baking temperature is too high, causes the wasting of resources, there is no
Other beneficial effects.
If drying time is less than 1h, owing to drying time is too short, cause dry insufficient, residual moisture；
And drying time is more than 2h, owing to drying time is long, causes the wasting of resources, there is no other beneficial effects.
Phosphoric acid solution concentration
In the present invention, being not particularly limited phosphoric acid solution concentration, usual phosphoric acid solution is 55-95wt%,
Preferably phosphoric acid solution is 65-85wt%, if phosphoric acid solution is less than 55wt%, due to phosphoric acid concentration mistake
Low, cause dipping insufficient, dipping effect is bad, and phosphoric acid solution is more than 95wt%, due to phosphoric acid concentration
Too high, cause dipping to generate non-targeted product, catalytic effect is impacted, there is no other beneficial effects.
Aluminum sulfate solution concentration
In the present invention, being not particularly limited aluminum sulfate solution concentration, usual aluminum sulfate solution is
15-25wt%, if aluminum sulfate solution is less than 15wt%, owing to aluminum sulfate concentration is too low, causes dipping effect
The most undesirable, load capacity is low, and aluminum sulfate solution is more than 25wt%, due to aluminum sulfate excessive concentration, causes
Affect phosphate impregnation effect, there is no other beneficial effects.
Introducing metallic element aluminum in dipping solution, catalyst, after high-temperature roasting, defines definite composition
Phosphate, each element is intermolecular synergism.Additionally, after introducing a certain amount of metallic element aluminum, catalysis
In agent, the acid content of high acid strength increases, and reactivity increases.
The mixing time of mixed solution
In the present invention, the mixing time of mixed solution is not particularly limited, generally stirs 6-12h；As
Really the mixing time in step (1) is less than 6h, owing to the time is too short, causes stirring insufficient, and reaction is not
Completely, and the mixing time of mixed solution is more than 12h, causes the time to waste, and there is no other beneficial effects.
The time of repose of mixed solution
In the present invention, the time of repose in mixed solution is not particularly limited, generally stands 6-12h；
If the time of repose in step (1) is less than 6h, owing to the time is too short, cause the response time not enough, shadow
Ringing catalytic effect, and the time of repose in mixed solution is more than 12h, causes the time to waste, there is no other has
Benefit effect.
The drying precipitate condition obtained after Li Xin
In the present invention the drying precipitate condition obtained after being centrifuged is not particularly limited, after being generally centrifuged
The drying precipitate condition arrived is at 100-140 DEG C of dry 6-12h；
If baking temperature is less than 100 DEG C, owing to baking temperature is too low, cause dry insufficient；And be dried
Temperature is more than 140 DEG C, owing to baking temperature is too high, causes the wasting of resources, there is no other beneficial effects.
If drying time is less than 6h, owing to drying time is too short, cause dry insufficient；And when being dried
Between more than 12h, owing to drying time is long, cause the wasting of resources, there is no other beneficial effects.
Roasting condition
In the present invention roasting condition is not particularly limited, generally in 300 DEG C-700 DEG C roasting 1-2h；
If sintering temperature is less than 300 DEG C, owing to sintering temperature is too low, cause decomposition reaction insufficient；And
Sintering temperature is more than 700 DEG C, owing to sintering temperature is too high, causes the wasting of resources, and easily generates other
By-product, there is no other beneficial effects.
If roasting time is less than 1h, owing to roasting time is too short, cause decomposition reaction insufficient；And roast
The burning time is more than 2h, owing to roasting time is long, causes the wasting of resources, and easily generates other by-products
Thing, there is no other beneficial effects.
Solid phosphoric acid catalyst granule
In the present invention, solid phosphoric acid catalyst granule is not particularly limited, generally screening 10-50 purpose
Granule forms solid phosphoric acid catalyst；
If solid phosphoric acid catalyst is less than 10 mesh, due to too small, cause and be not easily recycled after the reaction；And
Solid phosphoric acid catalyst is more than 50 mesh, due to excessive, cause effectively catalysis area to reduce, there is no it
His beneficial effect.
Diluent
In the present invention, being not particularly limited the kind of diluent, usual described diluent can be enumerated as
One or more in adiponitrile, glutaronitrile and pimelic dinitrile.
Phosphoric acid and sulfate quality amount ratio in mixed solution
In the present invention, phosphoric acid in mixed solution and sulfate quality amount ratio are not particularly limited, generally
Phosphoric acid solution and diatomaceous mass ratio are 10-15, and the addition of sulfate is kieselguhr quality
10%-15%.
Adipic acid and the mass ratio of diluent
In the present invention, being not particularly limited the mass ratio of adipic acid with diluent, usual adipic acid is with dilute
The mass ratio releasing agent is 1:2；
If adipic acid is less than 1:2 with the mass ratio of diluent, owing to the consumption of adipic acid is very few, cause anti-
Answering thing to reduce, yield reduces, and the mass ratio of adipic acid and diluent is more than 1:2, due to adipic acid consumption
Too much, causing waste, and reactant concentration is higher, dispersion effect is bad, there is no other beneficial effects.
Solid phosphoric acid consumption
In the present invention, being not particularly limited solid phosphoric acid consumption, usual solid phosphoric acid consumption is adipic acid
1%-2.5% with diluent gross mass；
If solid phosphoric acid consumption is less than adipic acid and the 1% of diluent gross mass, due to solid phosphoric acid consumption
Too small, cause catalytic effect bad, reaction yield reduces, and solid phosphoric acid consumption is more than adipic acid and dilution
The 2.5% of agent gross mass, owing to solid phosphoric acid consumption is too much, causes waste, there is no other beneficial effects.
Speed of agitator during reaction
In the present invention, being not particularly limited speed of agitator during reaction, generally during reaction, speed of agitator is
1000-2000r/min；
During reaction, speed of agitator is less than 1000r/min, owing to speed of agitator is too small during reaction, causes used time mistake
Grow, and reactant can not be uniformly distributed；And speed of agitator is more than 2000r/min when reacting, due to reaction
Time speed of agitator excessive, cause the wasting of resources, there is no other beneficial effects.
Heating-up temperature during reaction
In the present invention, being not particularly limited heating-up temperature during reaction, generally during reaction, heating-up temperature is
260℃-280℃；
If heating-up temperature is less than 260 DEG C during reaction, owing to during reaction, heating-up temperature is too low, cause reaction temperature
Degree not, reacts insufficient；And heating-up temperature is more than 280 DEG C when reacting, due to heating-up temperature mistake during reaction
Height, may generate side reaction, there is no other beneficial effects.
The ammonia flow being passed through during reaction
In the present invention, the ammonia flow being passed through during to reaction is not particularly limited, and is generally passed through during reaction
Ammonia flow is 150L/h-400L/h.
If the ammonia flow being passed through during reaction is less than 150L/h, the ammonia flow mistake being passed through during due to reaction
Little, cause response speed to slow down；And the ammonia flow being passed through when reacting is more than 400L/h, due to logical during reaction
The ammonia flow entered is excessive, may take away a part of heat, causes system unstable, and wastes raw material,
There is no other beneficial effects.
Response time
In the present invention, being not particularly limited the response time, the usual response time is 0.5-2h；If it is anti-
Less than 0.5h between Ying Shi, owing to the response time is too short, cause reaction insufficient；And the response time is more than 2h,
Owing to the response time is long, cause the wasting of resources, and easily generate by-product, there is no other beneficial effects.
[embodiment 1]
10g kieselguhr is dried under the baking oven of 120 DEG C 2h；Then impregnated in 120g mass percent dense
Degree is in the phosphoric acid solution of 75%, and adding 6g mass percent concentration is the aluminum sulfate solution of 20%, is formed
Mixed solution；12h is stood after mixed solution is stirred 12h；Mixed solution is centrifuged, the precipitate obtained
It is dried 12 hours in being placed on 120 DEG C of baking ovens；Dried precipitate is placed in pipe type calciner,
It is continually fed into N2, and roasting 2h at 400 DEG C, ultimately form solid phosphoric acid catalyst；After roasting
Solid phosphoric acid catalyst compression molding, obtains the granule of 20-40 mesh after screen cloth screens.
Solid phosphoric acid catalyst is applied as follows in adipic acid liquid phase method:
In aforesaid adipic acid liquid phase method technique, the input amount of adipic acid is 73g, the input amount of adiponitrile
For 146g, solid phosphoric acid input amount accounts for the 1.4% of the total input amount of reactant, and ammonia flow is 150L/h, stirs
Mixing rotating speed is 1500r/min, and reaction temperature is 270 DEG C.After finding reaction 60min, dehydration rate reaches
73.6%.
[embodiment 2]
Change the phosphoric acid concentration in the preparation process of embodiment 1 solid phosphoric acid into mass percent concentration 75%,
Phosphoric acid solution addition is 100g, and the copper-bath addition of mass percent concentration 20% is 5g, dry
Dry temperature is 100 DEG C, stands 6h after stirring 6h, and sintering temperature changes 600 DEG C into, and other conditions are constant,
Obtain solid phosphoric acid catalyst.
In aforesaid adipic acid liquid phase method technique, solid phosphoric acid input amount accounts for the total input amount of reactant
1.0%, speed of agitator is 1000r/min, and other process conditions are identical with example 1.Find reaction 60min
After, dehydration rate reaches 69.8%.
[embodiment 3]
Change the phosphoric acid concentration in the preparation process of embodiment 1 solid phosphoric acid into mass percent concentration 65%,
The addition of phosphoric acid solution is 150g, and the addition of aluminum sulfate solution is 7.5g, and sintering temperature changes 400 into
DEG C, baking temperature is 140 DEG C, and other conditions are constant, it is thus achieved that solid phosphoric acid catalyst.
In aforesaid adipic acid liquid phase method technique, the input amount of adipic acid is 200g, the input of adiponitrile
Amount is 400g, and solid phosphoric acid input amount accounts for the 2.1% of the total input amount of reactant, and ammonia flow is 400L/h,
Speed of agitator is 2000r/min, and reaction temperature is 280 DEG C.After finding reaction 60min, dehydration rate reaches
91.6%.
[embodiment 4]
Change the phosphoric acid concentration in the preparation process of embodiment 1 solid phosphoric acid into mass percent concentration 85%,
The addition of phosphoric acid solution is 150g, and the addition of aluminum sulfate solution is 7.5g, sintering temperature 500 DEG C, its
His condition is constant, it is thus achieved that solid phosphoric acid catalyst.
In aforesaid adipic acid liquid phase method technique, the input amount of adipic acid is 200g, the input of adiponitrile
Amount is 400g, and solid phosphoric acid input amount accounts for the 2.5% of the total input amount of reactant, and ammonia flow is 400L/h,
Speed of agitator is 1500r/min, and reaction temperature is 280 DEG C.After finding reaction 60min, dehydration rate reaches
94.7%.
[embodiment 5]
Change the phosphoric acid concentration in the preparation process of embodiment 1 solid phosphoric acid into mass percent concentration 55%,
Phosphoric acid solution addition is 100g, and (mass ratio is for the copper sulfate of mass percent concentration 20% and iron sulfate
1:1) solution addition is 5g, and sintering temperature changes 500 DEG C into, and other conditions are constant, it is thus achieved that solid phosphoric acid
Catalyst.
In aforesaid adipic acid liquid phase method technique, the input amount of adipic acid is 100g, the input of adiponitrile
Amount is 200g, and solid phosphoric acid input amount accounts for the 1.7% of the total input amount of reactant, and ammonia flow is 200L/h,
Speed of agitator is 1500r/min, and reaction temperature is 260 DEG C.After finding reaction 60min, dehydration rate reaches
56.6%.
[comparative example 1]
Being added without any catalyst, other process conditions are identical with embodiment 1, after reaction 60min, de-
Water rate is 26.7%.
[comparative example 2]
According to Zhang Yingnian, the report of peak et al. " research of Adiponitrile reaction macrokinetics ", industry
The liquid phosphoric acid catalyst concn of upper use is when 0.2%, and reaction effect is optimal.In process conditions and enforcement
In the reaction system that example 3 is identical, replace solid phosphoric acid catalyst, phosphoric acid with appropriate liquid phosphoric acid catalyst
Concentration controls 0.2%, and after reaction 60min, dehydration rate is 85.3%.
[comparative example 3]
Reaction condition is same as in Example 3, but is not added with aluminum sulfate, and after reaction 60min, dehydration rate reaches
89.3%.
Claims (10)
1. the method that an adipic acid liquid phase method produces adiponitrile, it is characterised in that catalyst is solid phosphoric acid
Catalyst, puts into adipic acid and diluent in reactor, heats and stir raw material, reach certain during reaction
It is passed through ammonia after temperature, after reaction after a while, generates product.
Adipic acid liquid phase method the most according to claim 1 produces the method for adiponitrile, it is characterised in that
Described solid phosphoric acid catalyst preparation method is: done under the baking oven of 100-140 DEG C by a certain amount of kieselguhr
After dry 1-2h, dry kieselguhr be impregnated in the phosphoric acid solution of 55%-95% of excess and 15-25wt%
In aluminum sulfate solution mixed solution, stir 6-12h, then stand 6-12h；After standing by mixed solution from
The heart, the precipitate obtained is dried 6-12 hour in 100-140 DEG C of baking oven；After drying precipitate is placed on
In pipe type calciner, N2At 300 DEG C-700 DEG C roasting 1-2h under protective condition；By its compression molding after cooling,
After screen cloth screens, obtain the granule of 10-50 mesh, form solid phosphoric acid catalyst.
Adipic acid liquid phase method the most according to claim 1 and 2 produces the method for adiponitrile, and its feature exists
In, described diluent is one or more in adiponitrile, glutaronitrile and pimelic dinitrile.
Adipic acid liquid phase method the most according to claim 2 produces the method for adiponitrile, it is characterised in that
Described phosphoric acid solution and diatomaceous mass ratio are 10-15, and the addition of aluminum sulfate is kieselguhr quality
10%-15%.
Adipic acid liquid phase method the most according to claim 1 and 2 produces the method for adiponitrile, and its feature exists
In, described adipic acid is 1:2 with the mass ratio of diluent.
Adipic acid liquid phase method the most according to claim 1 and 2 produces the method for adiponitrile, and its feature exists
In, solid phosphoric acid consumption is adipic acid and the 1%-2.5% of diluent gross mass.
Adipic acid liquid phase method the most according to claim 1 and 2 produces the method for adiponitrile, and its feature exists
In, during reaction, speed of agitator is 1000-2000r/min.
Adipic acid liquid phase method the most according to claim 1 and 2 produces the method for adiponitrile, and its feature exists
In, during reaction, heating-up temperature is 260 DEG C-280 DEG C.
Adipic acid liquid phase method the most according to claim 1 and 2 produces the method for adiponitrile, and its feature exists
In, the ammonia flow being passed through during reaction is 150L/h-400L/h.
Adipic acid liquid phase method the most according to claim 1 and 2 produces the method for adiponitrile, its feature
Being, the response time is 0.5-2h.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108409606A (en) * | 2018-06-01 | 2018-08-17 | 重庆华峰化工有限公司 | A kind of production system of adiponitrile |
| CN108821997A (en) * | 2018-06-01 | 2018-11-16 | 重庆华峰化工有限公司 | A kind of preparation method of adiponitrile and products thereof |
| CN109678756A (en) * | 2018-12-25 | 2019-04-26 | 上海交通大学 | A kind of reaction unit producing adiponitrile and method |
| CN111054436A (en) * | 2019-12-16 | 2020-04-24 | 中国科学院大连化学物理研究所 | Application of plasma modified phosphotungstic heteropoly acid in synthesis of adiponitrile from adipic acid |
| CN111056972A (en) * | 2019-12-16 | 2020-04-24 | 中国科学院大连化学物理研究所 | Application of alkyl quaternary phosphonium salt ionic liquid in synthesis of adiponitrile from adipic acid |
| CN113264848A (en) * | 2020-01-29 | 2021-08-17 | 英威达纺织（英国）有限公司 | Production of adiponitrile |
| CN115433104A (en) * | 2022-08-22 | 2022-12-06 | 沈阳开拓利思科技有限公司 | Preparation method of decanedinitrile |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108409606A (en) * | 2018-06-01 | 2018-08-17 | 重庆华峰化工有限公司 | A kind of production system of adiponitrile |
| CN108821997A (en) * | 2018-06-01 | 2018-11-16 | 重庆华峰化工有限公司 | A kind of preparation method of adiponitrile and products thereof |
| CN108409606B (en) * | 2018-06-01 | 2019-03-29 | 重庆华峰化工有限公司 | A kind of production system of adiponitrile |
| CN108821997B (en) * | 2018-06-01 | 2021-03-16 | 重庆华峰聚酰胺有限公司 | Preparation method of adiponitrile and product thereof |
| CN109678756A (en) * | 2018-12-25 | 2019-04-26 | 上海交通大学 | A kind of reaction unit producing adiponitrile and method |
| CN109678756B (en) * | 2018-12-25 | 2021-09-17 | 上海交通大学 | Reaction device and method for producing adiponitrile |
| CN111054436A (en) * | 2019-12-16 | 2020-04-24 | 中国科学院大连化学物理研究所 | Application of plasma modified phosphotungstic heteropoly acid in synthesis of adiponitrile from adipic acid |
| CN111056972A (en) * | 2019-12-16 | 2020-04-24 | 中国科学院大连化学物理研究所 | Application of alkyl quaternary phosphonium salt ionic liquid in synthesis of adiponitrile from adipic acid |
| CN111054436B (en) * | 2019-12-16 | 2021-04-23 | 中国科学院大连化学物理研究所 | Application of plasma modified phosphotungstic heteropoly acid in synthesis of adiponitrile from adipic acid |
| CN113264848A (en) * | 2020-01-29 | 2021-08-17 | 英威达纺织（英国）有限公司 | Production of adiponitrile |
| CN115433104A (en) * | 2022-08-22 | 2022-12-06 | 沈阳开拓利思科技有限公司 | Preparation method of decanedinitrile |
| CN115433104B (en) * | 2022-08-22 | 2024-02-06 | 沈阳开拓利思科技有限公司 | Preparation method of sebaconitrile |
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