CN103827076B - Equipment and the method for nitrification selectivity motility is given by azeotropic distillation - Google Patents
Equipment and the method for nitrification selectivity motility is given by azeotropic distillation Download PDFInfo
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- CN103827076B CN103827076B CN201280018865.XA CN201280018865A CN103827076B CN 103827076 B CN103827076 B CN 103827076B CN 201280018865 A CN201280018865 A CN 201280018865A CN 103827076 B CN103827076 B CN 103827076B
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- 238000000034 method Methods 0.000 title claims abstract description 41
- 238000010533 azeotropic distillation Methods 0.000 title description 14
- 230000004899 motility Effects 0.000 title description 2
- 150000007524 organic acids Chemical class 0.000 claims abstract description 71
- -1 alkyl acetate Chemical compound 0.000 claims abstract description 27
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 127
- 239000008346 aqueous phase Substances 0.000 claims description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 52
- 239000012071 phase Substances 0.000 claims description 42
- 208000035126 Facies Diseases 0.000 claims description 38
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 34
- DUWWHGPELOTTOE-UHFFFAOYSA-N n-(5-chloro-2,4-dimethoxyphenyl)-3-oxobutanamide Chemical compound COC1=CC(OC)=C(NC(=O)CC(C)=O)C=C1Cl DUWWHGPELOTTOE-UHFFFAOYSA-N 0.000 claims description 34
- 235000019260 propionic acid Nutrition 0.000 claims description 34
- 239000000047 product Substances 0.000 claims description 33
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 32
- MCSAJNNLRCFZED-UHFFFAOYSA-N nitroethane Chemical compound CC[N+]([O-])=O MCSAJNNLRCFZED-UHFFFAOYSA-N 0.000 claims description 25
- 239000004215 Carbon black (E152) Substances 0.000 claims description 18
- 229930195733 hydrocarbon Natural products 0.000 claims description 18
- 150000002430 hydrocarbons Chemical class 0.000 claims description 18
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 14
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 11
- 239000006227 byproduct Substances 0.000 claims description 11
- 229910017604 nitric acid Inorganic materials 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000001294 propane Substances 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 abstract description 14
- 239000012141 concentrate Substances 0.000 abstract description 10
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 37
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 37
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 37
- 239000002253 acid Substances 0.000 description 31
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 25
- 239000007791 liquid phase Substances 0.000 description 22
- 238000013461 design Methods 0.000 description 19
- 238000004821 distillation Methods 0.000 description 17
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 12
- 239000007789 gas Substances 0.000 description 11
- 229940011051 isopropyl acetate Drugs 0.000 description 11
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 10
- JSZOAYXJRCEYSX-UHFFFAOYSA-N 1-nitropropane Chemical compound CCC[N+]([O-])=O JSZOAYXJRCEYSX-UHFFFAOYSA-N 0.000 description 7
- FGLBSLMDCBOPQK-UHFFFAOYSA-N 2-nitropropane Chemical compound CC(C)[N+]([O-])=O FGLBSLMDCBOPQK-UHFFFAOYSA-N 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 238000012856 packing Methods 0.000 description 7
- DHPRWWYQIUXCQM-UHFFFAOYSA-N 2,2-dinitropropane Chemical compound [O-][N+](=O)C(C)(C)[N+]([O-])=O DHPRWWYQIUXCQM-UHFFFAOYSA-N 0.000 description 6
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 6
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 239000006096 absorbing agent Substances 0.000 description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 241000183024 Populus tremula Species 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 235000005985 organic acids Nutrition 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000004088 simulation Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 2
- 239000011260 aqueous acid Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- 239000001282 iso-butane Substances 0.000 description 2
- 235000013847 iso-butane Nutrition 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- NJNQUTDUIPVROZ-UHFFFAOYSA-N nitrocyclohexane Chemical compound [O-][N+](=O)C1CCCCC1 NJNQUTDUIPVROZ-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001272 nitrous oxide Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Abstract
The invention discloses and utilize alkyl acetate as entrainer with the method and apparatus concentrating at least one organic acid.Described method and apparatus uses same alkyl acetate to concentrate the mixture of organic acid as entrainer.
Description
Cross-Reference to Related Applications
This application claims the priority of India's provisional application No.1329/CHE/2011 submitted on April 18th, 2011, institute
State provisional application to be incorporated herein by with entire contents at this.
Technical field
The present invention relates to the azeotropic distillation in high pressure nitrification process.It is more particularly related to the nitroparaffin synthesis phase
Between when the organic acid stream produced comprises more than a kind of organic acid, the method for azeotropic removal of water and setting from described organic acid stream
Standby.
Background technology
In high pressure nitrification process, hydrocarbon such as propane and organic acids such as acetic acid, propanoic acid and/or butanoic acid is anti-with aqueous solution of nitric acid
Should, obtain product such as nitromethane, 1-nitropropane and 2-nitropropane.It addition, described method produces substantial amounts of water and one
A little organic acid.The many organic acid being fed into reactor do not convert in by the one way of reactor.Therefore, in order to by organic
Acid is recycled back in reactor, needs to remove many water.Because the relative volatility between acetic acid and water is low, therefore conventional
Distillation is power consumption and high cost.It addition, propanoic acid and n-butyric acie form low-boiling azeotrope with water, if using routine to steam
If evaporating, cause inevitably acid loss in overhead.May be recycled back to by needs it addition, exceed a kind of organic acid
To reactor.Therefore, to removing the economy of water from the organic acid stream comprising multiple organic acid and having the method for energy efficiency to deposit
At needs.
Summary of the invention
In one aspect, illustrative embodiment provides a method that, described method includes: by hydrocarbon charging and aqueous
The product stream comprising nitroparaffin and by-product with generation is reacted in charging in the reactor；Process described product stream to produce the first tower
Overhead stream and the first tower underflow, wherein said first tower top stream comprise nitroparaffin and described first tower underflow to comprise at least the first organic
Acid and water.Described method also includes supplying the first tower underflow to azeotrope tower；Alkyl acetate is used in azeotrope tower
As entrainer so that the first tower underflow is separated at least the second tower top stream and the second tower underflow, wherein said second tower top stream
Comprise alkyl acetate and water and wherein said second tower underflow comprises the first organic acid；By described second in phase separator
Tower top flow separation becomes organic facies and aqueous phase, described organic facies to comprise alkyl acetate；And at least by described organic facies
Divide and return to described azeotrope tower.
In yet another aspect, illustrative embodiment provides a method that, described method is included in high pressure nitrification process
Middle hydrocarbon charging charging with aqueous reacts the product stream comprising nitroparaffin and by-product with generation, wherein said water in the reactor
Property charging comprise water, nitric acid, at least one first organic acid and at least one the second organic acid；Process described product stream to produce
First tower top stream and the first tower underflow, wherein said first tower top stream comprises nitroparaffin and described first tower underflow comprises described
First organic acid, the second organic acid and water.Described method also includes supplying the first tower underflow to azeotrope tower；At azeotropic distillation
Tower use alkyl acetate as entrainer so that the first tower underflow is separated at least the second tower top stream and the second tower underflow,
Wherein said second tower top stream comprises alkyl acetate and water and wherein said second tower underflow comprises the first organic acid and
Two organic acid；Organic facies and aqueous phase, described organic facies is become to comprise acetic acid alkane described second tower top flow separation in phase separator
Base ester；And described organic facies returned to described azeotrope tower at least partially.
In yet another aspect, illustrative embodiment provides a kind of equipment, and described equipment includes: reactor, is used for
Hydrocarbon charging and aqueous charging are reacted to produce the product stream comprising nitroparaffin and by-product by high pressure nitrification process, wherein said
Aqueous charging comprises water, nitric acid, at least one first organic acid and at least one the second organic acid；At least one degasser, uses
In product stream is deaerated to produce liquid stream；With at least one strip (stripping) equipment, for by described liquid flow from
Become the first tower top stream and the first tower underflow, wherein said first tower top stream to comprise nitroparaffin and described first tower underflow comprises institute
State the first organic acid, the second organic acid and water.Described equipment also includes azeotrope tower, and it is configured to use alkyl acetate
As entrainer, so that the first tower underflow to be separated into the second tower top stream and the second tower underflow, wherein said second tower top stream comprises
Alkyl acetate and water, and wherein said second tower underflow comprises described first organic acid and described second organic acid；And phase
Separator, it is configured to become organic facies and aqueous phase, described organic facies to comprise described acetic acid alkane described second tower top flow separation
Base ester.
Aforementioned summary is merely exemplary, and is not intended to limit by any way.Except described above illustrative
Outside aspect, embodiment and feature, by with reference to accompanying drawing and detailed description below, other aspect, embodiment and spy
Levy and will be apparent from.
Accompanying drawing explanation
Fig. 1 is according to illustrated embodiment, for removing the schematic diagram of the equipment of water from organic acid soln.
Fig. 2 is according to illustrated embodiment, for producing nitroparaffin and removing the showing of equipment of water from organic acid soln
It is intended to.
Fig. 3 is the schematic diagram of the distillation column for embodiment 7.
Fig. 4 is the schematic diagram of the distillation column for embodiment 7, it is shown that the position of hygrosensor.
Fig. 5 is the temperature profile of embodiment 7.
Detailed description of the invention
In one aspect, it is provided that use alkyl acetate as entrainer so that from organic sour water in azeotrope tower
The method removing water in solution.Fig. 1 shows the equipment 100 removing water from aqueous solutions of organic acids.First aqueous phase 101 can be
Merge with organic facies 102 at first control valve 103, form feed stream 104.First aqueous phase 101 can comprise water and at least one
Organic acid.Described organic acid can be acetic acid, propanoic acid, butanoic acid, caproic acid, other carboxylic acids or its any combination.In the side of being preferable to carry out
In formula, the first aqueous phase 101 comprises the organic acid that at least two is different.Such as, the first aqueous phase 101 can comprise acetic acid and propanoic acid,
Or propanoic acid and butanoic acid.In other preferred implementations, the first aqueous phase 101 comprises at least three kinds of different organic acid.Such as,
One aqueous phase 101 can comprise acetic acid, propanoic acid and butanoic acid.Described organic facies 102 can comprise at least one alkyl acetate.Described
Alkyl acetate can be such as isopropyl acetate, n-butyl acetate or isobutyl acetate.
Feed stream 104 can be supplied to azeotrope tower 105.In alternate embodiments, the first aqueous phase 101 and organic facies
102 can be supplied directly to azeotrope tower 105.Azeotrope tower 105 can be such as heterogeneous azeotropic distillation (HAD) tower
(acid drying tower (ADC)).Azeotrope tower 105 can include condenser 106 and reboiler 107.
In azeotrope tower 105, alkyl acetate can serve as entrainer so that feed stream 104 is separated at least tower
Overhead stream 108 and tower underflow 109.Tower top stream 108 can comprise described alkyl acetate and water.Tower underflow 109 can comprise described
At least one organic acid.The concentration of organic acid described in tower underflow 109 can be about 70 weight % or bigger, more preferably from about 80 weights
Amount % or bigger, and most preferably from about 85 weight % or bigger.Additionally, the concentration of organic acid can be about 98 described in tower underflow 109
Weight % or less, more preferably from about 95 weight % or less, and most preferably from about 90 weight % or less.
Tower top stream 108 can enter phase separator 110.Phase separator 110 can be decanter.Phase separator 110 is permissible
Tower top stream 108 is separated into gas phase 111, organic facies 112 and the second aqueous phase 113.At least some of described organic facies 112 is permissible
As organic facies 102 by the second control valve 114, described organic facies 102 may return to distillation column 104 or the first control valve
103.Second aqueous phase 113 can be divided into recirculation aqueous phase 116 in allotter (divider) 115 and discharge aqueous phase 117.Again
Circulation aqueous phase 116 may return to distillation column 105.Second aqueous phase 113 returns to distillation column 105 as recirculation aqueous phase 116
Percentage ratio can be about 40% or bigger, more preferably from about 44% or bigger, and most preferably from about 45% or bigger.Additionally, the second aqueous phase
113 return to the percentage ratio of distillation column 105 as recirculation aqueous phase 116 can be about 60% or less, more preferably from about 54% or more
Little, and most preferably from about 47% or less.
Add entrainer and can add phase separator 110 to by the supplementary stream 118 of entrainer.Can add and add entrainer
Amount, to compensate in tower underflow 109 and/or the amount of discharging in aqueous phase 117 entrainer removing or losing.
Fig. 2 shows the equipment 200 removing water from aqueous solutions of organic acids, and wherein said organic acid soln is high pressure nitrification
The by-product of method.Described high pressure nitrification process uses mixed phase reactor assembly to include both liquid phase and steam phase.Use relatively
High operation pressure produces significant liquid phase in described reactor.Hydrocarbon charging 201 and aqueous charging 202 can be introduced into reaction
In device 203.Hydrocarbon charging 201 can include but not limited to propane, hexamethylene, iso-butane or normal octane.Aqueous charging 202 can be wrapped
Include, but be not limited to, water, nitric acid and at least one organic acid, such as acetic acid, propanoic acid, butanoic acid, caproic acid, other carboxylic acid or its
What combination.In a preferred embodiment, aqueous charging 201 comprises the organic acid that at least two is different.Such as, described aqueous is entered
Material 201 can comprise acetic acid and propanoic acid or propanoic acid and butanoic acid.In other preferred implementation, aqueous charging 201 comprise to
Few three kinds of different organic acid.Such as, described aqueous charging 201 can comprise acetic acid, propanoic acid and butanoic acid.
Hydrocarbon feed 201 and aqueous charging 202 can be reacted in reactor 203 under reactor pressure and reaction temperature,
Allow to form the reacting product stream 204 comprising Nitrated compounds and by-product.Reacting product stream 204 can comprise at least one
Plant product nitroparaffin.Such as, when hydrocarbon charging 201 comprises propane, reacting product stream 204 can include one or more nitros third
Alkane, includes but not limited to 1-nitropropane, 2-nitropropane and/or 2,2-dinitro-propane.When hydrocarbon charging 201 comprises hexamethylene
During alkane, reacting product stream 204 can comprise nitrocyclohexane.When hydrocarbon charging 201 comprises iso-butane, reacting product stream 204 can
To comprise nitro-ter-butane.When hydrocarbon charging 201 comprises normal octane, reacting product stream can comprise nitro normal octane.
Hydrocarbon feed 201 and aqueous solution of nitric acid 202 can mix before entering in reactor 203, or part mixing, or
Person, they can single add, and mixes in reactor 203.It addition, described hydrocarbon charging 201 and aqueous solution of nitric acid 202,
It is no matter together or single interpolation, can preheat before entering in reactor 203.
Aqueous solution of nitric acid in aqueous charging 202 can with containing at least about 10 weight %, more preferably at least about 15 weight %,
Aqueous acid form described in most preferably at least about 20 weight % is shipped to reactor 203.Additionally, described solution can be containing few
In about 50 weight %, more preferably less than about 40 weight % and the described acid of most preferably less than about 35 weight %.At other embodiments
In, salpeter solution can be containing the described acid between about 15 and about 40 weight %.In other embodiments, salpeter solution is permissible
Containing the described acid between about 18 and about 35 weight.
Organic acid in aqueous charging 202 can be with containing described at least about 15 weight %, more preferably at least about 40 weight %
Organic aqueous acid form is shipped to reactor 203.
Hydrocarbon charging 201 can be at least about 0.3:1, more preferably at least about 0.5:1 with the mol ratio of aqueous solution of nitric acid 202.
In described high pressure nitrification process, reactor pressure can be at least about 3.4x106Pascal (500psi), more preferably
At least about 6.8x106Pascal (1000psi), and most preferably at least about 8.3x106Pascal (1200psi).Some embodiment party
In formula, described pressure can be about 11.0x106Pascal (1600psi) or less, more preferably from about 10.3x106Pascal
(1500psi) or less, most preferably from about 9.7x106Pascal (1400psi) or less.In other embodiments, described pressure
Power can be at about 6.8x106Pascal (1000psi) and 9.7x106(1400psi) between Pascal.Known in the art
Various methods may be used for being maintained in desired scope described pressure, including such as by use back pressure regulator.
Reaction temperature in reactor 203 can control (heat such as produced) with heat-exchange fluid or utilization reaction to extremely
Few about 140 degrees Celsius and less than about 325 degrees Celsius.In other embodiments, described temperature can be at least about 215 degrees Celsius
And less than about 325 degrees Celsius.In some embodiments, described temperature can be at least about 180 degree, at least about 200 degree, at least
About 230 degree, or at least about 240 degree.In other embodiments, described temperature can be less than about 290 degree, less than about 280 degree,
Less than about 270 degree, or less than about 250 degree.In other embodiments, described temperature can about 200 and 250 degrees Celsius it
Between.In still other embodiment, described temperature can be between about 215 and 280 degrees Celsius, or about 220 and 270 degrees Celsius
Between.
The reactant time of staying in reactor 203 can preferably at least about 30 seconds, more preferably at least about 90 seconds.Stop
Time can control in various manners, and described mode includes such as by length and/or the width of reactor or being filled out by use
Fill material.The time of staying can be determined divided by inlet flow rate by reactor volume.
Reactor 203 can be that downflow system constructs reactor.It is to say, can dispose preferred elongated and rectilinear form,
The reactor of such as tubulose so that reactant by reactor head or near import add, then be enough to allow
Reaction occurs and is formed to expect that the time of staying of product is downward through described reactor.Product mixtures can be by reactor
At Di Bu or neighbouring outlet is collected.
In downflow system constructs, operate reactor provide some advantage exceeding prior art systems, prior art systems
Typically utilize horizontal, up flow type, coiled or batch autoclave type equipment.Especially, with such prior art systems phase
Ratio, the Nitrated compounds that the downflow system structure of the present invention provides contains the low-level oxidized byproduct of comparison.
It is not intended to be bound to any particular theory, it is believed that the advantage of downflow reactor can be by essentially from it
The amount of liquid phase and minimizing residence time in reactor.Described liquid phase typically contains the mol ratio of low hydrocarbon and nitric acid.This low
Mol ratio beneficially oxidation chemistry and sacrifice nitrification, therefore oxidation occur mainly in liquid phase.At downflow reactor (also referred to as
For trickle bed reactor) in, gas is continuous phase, and liquid downward drip-flow reactor wall or filler.Therefore, downflow system structure is anti-
Answering in device, the amount of liquid phase is maintained at low-level, and therefore oxidation chemistry is minimized.
On the contrary, in upflow-type reactor (also referred to as in bubble tower), liquid is that (and bubble rises rapidly logical continuous phase
Cross described Continuous Liquid Phase).Therefore, liquid holdup is maximized by upflow-type reactor.Because, as it has been described above, oxidation occurs mainly in
In liquid phase, therefore upflow-type reactor maximises the formation of oxidized byproduct.Similarly, compared with downflow reactor, dish
Tubular type and horizontal reactor structure too increase liquid residence time, therefore add oxidation chemistry.Coil pipe type reactor
Another shortcoming is because being difficult to manufacture commercial scale reactor with this shape, so they are not well suited for commercial scale life
Produce.
Reactor 203 can also be filled with packing material, to improve reactant mixing and heat transfer and/or to change reactor
Volume.Such as expecting to increase in reacting product stream 2, in the propane nitrification of 2-dinitro-propane concentration, filling out of reactor
Fill and be probably preferably.Suitably packing material can include such as bead, irregular filler or structured packing, the most generally
Those used in distilling apparatus.Other packing materials are known in the art and can use.Reactor 203 also may be used
To be unfilled reactor.
Then reacting product stream 204 can enter the first degasser 205.First degasser 205 can be by reacting product stream
204 are separated into the first gas phase 206 and the first liquid phase 207.First gas phase 206 can be sent to absorber 208.Absorber 208 is permissible
Circulating water flow 209 is utilized to absorb any nitroparaffin in the first gas phase 206 to form the second gas phase 210 and second liquid phase
211.In illustrative embodiment, the recirculated water in circulating water flow 209 can nitroparaffin removal process recirculation downstream.
Second liquid phase 211 can be sent to the first stripping apparatus 212 to reclaim at least one product nitroparaffin described.First vapour
Carry equipment 212 and can comprise the first condenser 213 and the first reboiler 214.First stripping apparatus 212 can be from second liquid phase
211 stripped oil soluble components so that form the second gas phase the 215, first oil phase 216 and the first aqueous phase 217.First oil phase 216 can
To be sent to the first separator 218.First separator 218 can be such as conventional distil-lation tower.First separator 218 can be by first
Oil phase 218 is separated at least the second oil phase 219 and the second aqueous phase 220.Second oil phase 219 can comprise at least one product described
Nitroparaffin.
Then the first liquid phase 207 from the first degasser 205 can enter the second degasser 221.Second degasser 221
First liquid phase 207 can be separated into the 3rd gas phase 222 and the 3rd liquid phase 223.In some illustrated embodiment, high concentration
Acetic acid can assist solubilising nitroparaffin product so that produce single liquid phase 223 rather than oil phase and aqueous phase.Described liquid phase 223
At least one product nitroparaffin described and at least one organic acid can be comprised.
Then liquid phase 223 can be sent to the second stripping apparatus 224.Second stripping apparatus 224 can comprise the second condensation
Device 225 and the second reboiler 226.Second stripping apparatus 224 can be from the 3rd liquid phase 223 stripped oil soluble component so that is formed
4th gas phase the 227, the 3rd oil phase 228 and the 3rd aqueous phase 229.3rd oil phase 228 can be sent to the second separator 230.Second
Separator 230 can be such as conventional distil-lation tower.3rd oil phase 228 can be separated at least the 4th oil by the second separator 230
Mutually 231 and the 4th aqueous phase 232.3rd oil phase 231 can comprise at least one product nitroparaffin described.
3rd aqueous phase 229 can comprise water and at least one organic acid.Described organic acid can be acetic acid, propanoic acid, butanoic acid,
Other carboxylic acids or its any combination.In a preferred embodiment, the 3rd aqueous phase 229 comprises at least two organic acid.At other
In preferred implementation, the 3rd aqueous phase 229 comprises at least three kinds of different organic acid.3rd aqueous phase 229 can control first
Merge with organic facies 233 at valve 234, to form feed stream 235.Organic stream 233 can comprise at least one alkyl acetate.Institute
Stating alkyl acetate can be such as isopropyl acetate, n-butyl acetate or isobutyl acetate.
Feed stream 235 can be sent to distillation column 236, such as heterogeneous azeotropic distillation column.Heterogeneous azeotropic distillation column can
To be used for separating the close mixture of relative volatility and also for separately azeotropic mixture.Distillation column 236 can comprise the 3rd
Condenser 237 and the 3rd reboiler 238.In distillation column 236, alkyl acetate can serve as entrainer so that feed stream 235
It is separated at least tower top stream 239 and tower underflow 240.Tower top stream 239 can comprise alkyl acetate and water.Tower underflow 240 is permissible
Comprise organic acid.Organic acid concentration in tower underflow 240 can be about 70 weight % or bigger, more preferably from about 80 weight % or more
Greatly, and most preferably from about 85 weight % or bigger.Additionally, the organic acid concentration in tower underflow 240 can be about 98 weight % or less,
More preferably from about 95 weight % or less, and most preferably from about 90 weight % or less.Tower underflow 240 can be as in hydrocarbon charging 201
Organic acid dilute agent returns to reactor 203.In alternate embodiments, tower underflow 240 may be used for other purposes, such as, use
During other.
Tower top stream 239 can enter phase separator 241.Phase separator 241 can be decanter.Phase separator 241 is permissible
Tower top stream 229 is separated into the 5th gas phase 242, organic facies 243 and the 4th aqueous phase 244.At least some of described organic facies 244
Can be as organic facies 233 by the second control valve 245, described organic facies 233 may return to distillation column 236 or first and controls
Valve 234.4th aqueous phase 244 can be divided into recirculation aqueous phase 247 in allotter 246 and discharge aqueous phase 248.Recirculation aqueous phase
247 may return to distillation column 236.4th aqueous phase 244 returns to the percentage ratio of distillation column 236 as recirculation aqueous phase 247 can
Being about 40% or bigger, more preferably from about 44% or bigger, and most preferably from about 45% or bigger.Additionally, the 4th aqueous phase 244 is as again
Circulation aqueous phase 247 returns to the percentage ratio of distillation column 236 and can be about 60% or less, more preferably from about 54% or less, and optimum
Choosing about 47% or less.
Add entrainer and can add phase separator 241 to by the supplementary stream 249 of entrainer.The azeotropic added can be added
The amount of agent compensates the amount of the entrainer removing or losing in tower underflow 240 and/or discharge aqueous phase 248.
Embodiment
Show various embodiment.Embodiment 1-6 utilizes ASPEN computer assisted procedures simulation softward (Aspen
Technology, Incorporated, Burlington, Massachusetts) produce, described software uses the physics measured
The data base of character is used for engineering calculation.Embodiment 7 is from the test of research and development factory.
Simulation
Embodiment 1-6 utilizes ASPEN computer assisted procedures simulation softward to produce.Propane, nitric acid and organic acid are in reaction
In device react, produce comprise nitroparaffin (nitromethane, 1-nitropropane, 2-nitropropane, 2,2-dinitro-propane, nitro second
Alkane) and the product stream of oxidized byproduct (acetic acid, propanoic acid, butanoic acid).Described product stream also comprises waste gas, such as nitrous oxide, oxygen
Change nitrogen, carbon dioxide, carbon monoxide, unconverted propane and water.
Product stream deaerates in two continuous print degassers.Then air-flow from the first degasser separates in absorber
(carrying out scrubbing with recirculated water, such as water from the step in the nitroparaffin removal process of downstream) so that form gas phase and aqueous phase.
Aqueous phase from absorber is sent to the first stripping apparatus, removes a small amount of recovery nitroparaffins wherein.From the second degassing
The aqueous phase of device and the aqueous phase from the first stripping apparatus are sent to the second stripping apparatus.There, from aqueous phase, strip nitroparaffin,
The bottomsstream making described stripping apparatus comprises the organic acid of water and dissolving.The bottomsstream from the second stripping apparatus
Generally comprising about 60 weight % organic acid, it is the denseest before being recycled to reactor as organic acid dilute agent
It is reduced to about 90 weight % organic acid.
Table 1 below shows the azeotropic composition of the various alkyl acetates as entrainer.Entrainer is with feed rate ratio together
In boiling composition, the mass percent of water is inversely proportional to.Therefore, in alkyl acetate, the amount of the entrainer of needs is along with carbon chain lengths
Increase and reduce.
Table 1. is for the entrainer of water-separated from acetic acid
Embodiment 1:Isopropyl acetate is utilized to concentrate the heterogeneous azeotropic distillation scheme of acetic acid
This example demonstrates use isopropyl acetate as entrainer.Heterogeneous azeotropic distillation column (HAD) is designed to
Obtain expecting the acetic acid product of purity at the bottom of tower, obtain isopropyl acetate/water azeotropic mixture simultaneously as overhead.Tower top
Distillate flow forms two kinds of liquid phase organic faciess and aqueous phase when condensation and decant.Described organic facies mainly comprises isopropyl acetate
Ester, and described aqueous phase mainly comprises water (anacidity aqueous flow (AFAS)).The backflow of whole organic facies returns to HAD tower, to provide foot
Enough isopropyl acetates serve as entrainer.Then it mix with feed stream, and is commonly fed HAD tower.Described aqueous phase is from described
System is extracted out, for processing further or discharge.If described organic backflow does not reaches meets described tower specification, then a part
Aqueous phase can be recirculated back to described tower.
The design basis of HAD tower shows in table 2 below.
The design basis aqueous acetic acid charging of table 2.HAD tower
| Work pressure | 101,325 Pascals (1 atmospheric pressure) |
| Flow kg/h (lb/h) | Charging |
| Acetic acid | 19907(43849) |
| Nitromethane | 29(63) |
| Nitroethane | 8(17) |
| 2-nitropropane | 36(80) |
| 1-nitropropane | 12(26) |
| 2,2-dinitro-propane | 44(97) |
| Water | 13191(29056) |
| Acid recovery percentage ratio | >99% |
HAD tower is made up of 40 equilibrium stages, and wherein the aqueous acetic acid stream of 60 weight % (evaporates from the bottom of the tower of the second stripper
Go out thing) it is fed into the 7th grade from tower top.Overhead from HAD tower is condensed, and is then separated, and produces organic facies and water
Phase.Whole organic facies and 10% aqueous-phase reflux return to the tower top of HAD.Described tower is with the 98% acetic acid response rate in the bottomsstream
Design specification under operate.Table 3 below shows in the case of isopropyl acetate is as entrainer, the input/output stream of HAD tower
Details.
Table 3 uses isopropyl acetate as the details of HAD tower stream during entrainer
Embodiment 2:N-butyl acetate is utilized to concentrate the heterogeneous azeotropic distillation scheme of acetic acid
This example demonstrates use n-butyl acetate as entrainer.Obtain at the bottom of HAD Deethanizer design Cheng Ta expecting purity
Acetic acid product, obtain n-butyl acetate/water azeotropic mixture simultaneously as overhead.Column overhead stream condensation and
Two kinds of liquid phase organic faciess and aqueous phase is formed during decant.Described organic facies mainly comprises n-butyl acetate, and described aqueous phase master
Water to be comprised (anacidity aqueous flow (AFAS)).The backflow of whole organic facies returns to HAD tower, to provide enough n-butyl acetates to fill
Work as entrainer.Then it mix with feed stream, is commonly fed HAD tower.Described aqueous phase is extracted out from described system, is used for into one
Step processes or discharge.If described organic backflow does not reaches meets described tower specification, the most a part of aqueous phase can be recirculated back to institute
State tower.
HAD tower is made up of 40 equilibrium stages, and wherein the aqueous acetic acid stream of 60 weight % (evaporates from the bottom of the tower of the second stripper
Go out thing) it is fed into the 4th grade from tower top.Overhead from HAD tower is condensed, and is then separated, and produces organic facies and water
Phase.Whole organic facies and 20% aqueous-phase reflux return to the tower top of HAD tower.Table 4 below shows at n-butyl acetate as entrainer
In the case of, the input/output stream details of HAD tower.
Table 4 uses n-butyl acetate as the details of HAD tower stream during entrainer
Embodiment 3:Isobutyl acetate is utilized to concentrate the heterogeneous azeotropic distillation scheme of acetic acid
This example demonstrates use isobutyl acetate as entrainer.Obtain at the bottom of HAD Deethanizer design Cheng Ta expecting purity
Acetic acid product, obtain isobutyl acetate/water azeotropic mixture simultaneously as overhead.Column overhead stream condensation and
Two kinds of liquid phase organic faciess and aqueous phase is formed during decant.Described organic facies mainly comprises isobutyl acetate, and described aqueous phase master
Water to be comprised (anacidity aqueous flow (AFAS)).The backflow of whole organic facies returns to drying tower, to provide enough isobutyl acetate
Serve as entrainer.Then it mix with feed stream, is commonly fed HAD tower.Described aqueous phase is extracted out from described system, be used for into
One step processes or discharge.If described organic backflow does not reaches meets described tower specification, the most a part of aqueous phase can be recirculated back to
Described tower.
HAD tower is made up of 40 equilibrium stages, and wherein the aqueous acetic acid stream of 60 weight % (evaporates from the bottom of the tower of the second stripper
Go out thing) it is fed into the 16th grade from tower top.The overhead coming from HAD tower is condensed, and is then separated, and produces organic facies and water
Phase.Whole organic facies and 4% aqueous-phase reflux return to the tower top of HAD tower.Table 5 below shows at isobutyl acetate as entrainer
In the case of, the input/output stream details of HAD tower.
Table 5 uses isobutyl acetate as the details of HAD tower stream during entrainer
Table 6 below compares the design parameter of the HAD tower using isopropyl acetate, n-butyl acetate and isobutyl acetate.?
In the case of isopropyl acetate, due to it azeotropic form in water content (10 weight %) than isobutyl acetate and n-butyl acetate
(respectively 16 and 27 weight %) is low, so entrainer is maximum with feed rate ratio.Need in the case of n-butyl acetate boils again
Device thermic load is minimum；But the acetic acid of loss is the highest in the middle of described three kinds of candidate's entrainers in AFAS stream.Further, any acetic acid
N-butyl flow back into reactor and the generation of undesired by-product, described by-product may be caused can to pollute end product
This situation is not had when with isobutyl acetate.
Table 6 is for the comparison of the HAD Deethanizer design parameter of isopropyl acetate, n-butyl acetate and isobutyl acetate
Embodiment 4:Isobutyl acetate is utilized to concentrate aqueous mixed acid stream heterogeneous common comprising acetic acid, propanoic acid and butanoic acid
Boiling distillation scheme
This example demonstrates and use isobutyl acetate as entrainer, comprise acetic acid, propanoic acid and butanoic acid for concentrating
Aqueous mixed acid feed stream.The design basis of HAD tower shows in table 7 below.
The design basis aqueous mixed acid charging of table 7.HAD tower
| Work pressure | 101,325 Pascals (1 atmospheric pressure) |
| Flow kg/h (lb/h) | Charging |
| Acetic acid | 13338(29380) |
| Propanoic acid | 3284(7233) |
| Butanoic acid | 3284(7233) |
| Nitromethane | 29(63) |
| Nitroethane | 8(17) |
| 2-nitropropane | 36(80) |
| 1-nitropropane | 12(26) |
| 2,2-dinitro-propane | 44(97) |
| Water | 13191(29056) |
| Total acid recovery percentage ratio | >99% |
Table 8 below shows in the case of isobutyl acetate is as entrainer, the input of the HAD tower of mixed acid charging/defeated
Go out to flow details.
Table 8 isobutyl acetate feeds as HAD tower stream details mixed acid (acetic acid: propanoic acid: butanoic acid) of entrainer
Table 9 below shows the design parameter using isobutyl acetate to concentrate the HAD tower that mixed acid feeds.At described HAD tower
Middle use isobutyl acetate reaches total acid recovering rate of about 99.5% as entrainer.
Table 9 use isobutyl acetate as entrainer, for the design parameter of the HAD tower of mixed acid charging
Embodiment 5:Isobutyl acetate is utilized to concentrate the aqueous mixed acid stream comprising 50 weight % acetic acid and 50 weight % propanoic acid
Heterogeneous azeotropic distillation scheme
This example demonstrates and use isobutyl acetate as entrainer, comprise 50:50(weight % for concentration) ratio
The aqueous mixed acid feed stream of acetic acid and propanoic acid.The design basis of HAD tower shows in table 10 below.
Design basis mixed acid charging (acetic acid: propanoic acid) of table 10 HAD tower
| Work pressure | 101,325 Pascals (1 atmospheric pressure) |
| Flow kg/h (lb/h) | Charging |
| Acetic acid | 9954(21925) |
| Propanoic acid | 9964(21925) |
| Nitromethane | 29(63) |
| Nitroethane | 8(17) |
| 2-nitropropane | 36(80) |
| 1-nitropropane | 12(26) |
| 2,2-dinitro-propane | 44(97) |
| Water | 13191(29056) |
| Total acid recovery percentage ratio | >99% |
Table 11 below shows in the case of isobutyl acetate is as entrainer, the HAD of mixed acid charging (acetic acid: propanoic acid)
The input/output stream details of tower
Table 11 isobutyl acetate feeds as HAD tower stream details mixed acid (acetic acid: propanoic acid) of entrainer
Table 12 below shows and uses isobutyl acetate to concentrate the design parameter that mixed acid feeds the HAD tower of (acetic acid: propanoic acid).
Isobutyl acetate is used to reach total acid recovering rate of about 99.6% as entrainer in described HAD tower.
Table 12 uses isobutyl acetate as the design parameter of the HAD tower of entrainer
Embodiment 6:Utilize isobutyl acetate to concentrate and comprise 50 weight % propanoic acid and the aqueous mixed acid of 50 weight % n-butyric acies
The heterogeneous azeotropic distillation scheme of stream
This example demonstrates and use isobutyl acetate as entrainer, comprise 50:50(weight % for concentration) ratio
The aqueous mixed acid feed stream of propanoic acid and n-butyric acie.The design basis of HAD tower shows in table 13 below.
Design basis mixed acid charging (propanoic acid: n-butyric acie) of table 13 HAD tower
| Work pressure | 101,325 Pascals (1 atmospheric pressure) |
| Flow kg/h (lb/h) | Charging |
| Propanoic acid | 9954(21925) |
| N-butyric acie | 9964(21925) |
| Nitromethane | 29(63) |
| Nitroethane | 8(17) |
| 2-nitropropane | 36(80) |
| 1-nitropropane | 12(26) |
| 2,2-dinitro-propane | 44(97) |
| Water | 13191(29056) |
| Total acid recovery percentage ratio | >99% |
Table 14 below shows in the case of isobutyl acetate is as entrainer, mixed acid charging (propanoic acid: n-butyric acie)
The input/output stream details of HAD tower.
Table 14 isobutyl acetate feeds as HAD tower stream details mixed acid (propanoic acid: n-butyric acie) of entrainer
Table 15 below shows the design using isobutyl acetate to concentrate the HAD tower that mixed acid charging (propanoic acid: n-butyric acie) flows
Parameter.Isobutyl acetate is used to reach total acid recovering rate of about 99.7% as entrainer in described HAD tower.
Table 15 uses isobutyl acetate to feed as the design parameter (propanoic acid: n-butyric acie) of the HAD tower of entrainer
Test example
Also illustrate to use isobutyl acetate as entrainer using test.Embodiment 7 is at continuous still tower as shown in Figure 3
On complete.This tower is made up of 316L rustless steel.Tower internal diameter is 6.36 inches and about 24 feet high.Filler is by four 5 ' 3.3 "
The 1T Intalox of sectionStructured packing forms.Temperature Distribution uses the hygrosensor survey being located substantially in the middle of each packing section
Amount, as shown in Figure 4.Distribution plate is between each packing section, to keep liquid distribution.Described distribution plate also allows for feed entrance point and becomes
Dynamic.Described tower is equipped with pump around reboiler.Use 2.8x106Pascal (40psi) steam heating.Overhead product makes
Use cooling water condensation.Decanter can be used to be separated and reflux from the single phase of heteroazeotrope.Described tower can
With in vacuum (5mm Hg) until 5.2x105Operate under the pressure of Pascal (75psi).Preparation about 60 weight % acetic acid and 40
The incoming mixture of weight % deionized water tests the isobutyl acetate performance as entrainer.
Embodiment 7:
Table 16 below shows if having allowed more isobutyl acetate in tower underflow, by column overhead stream
The ability that minimizes of acetic loss.
Table 16
Fig. 5 shows the Temperature Distribution in table 16 during experiment.
Although the preferred implementation that the present invention has been described above according to it is described, but it can be in the disclosure
Modify in the spirit and scope held.Therefore the application is intended to utilize General Principle disclosed herein, to the present invention's
Any change, application or improvement.Additionally, the application is intended to still at the known of the technical field of the invention or usually real
In the range of trampling and fall within the of this disclosure this kind of deviation in the restriction of following claims.
Claims (8)
1. a method, described method includes:
By hydrocarbon charging and aqueous charging in the reactor at least 140 degrees Celsius and be less than the reaction temperature and extremely of 325 degrees Celsius
Few 6.8x106In high pressure nitrification process, the product comprising nitroparaffin and by-product with generation is reacted under the reaction pressure of Pascal
Stream,
The charging of wherein said aqueous comprises water, 10 and 35 nitric acid between weight % and the first organic acid,
The charging of wherein said liquid waterborne comprises the first organic acid of at least 40 weight %；
Process described product stream to produce the first tower top stream and the first tower underflow, wherein said first tower top stream comprise nitroparaffin and
Described first tower underflow comprises the most described first organic acid and water；
At least some of of the first tower underflow is supplied to azeotrope tower；
Use alkyl acetate as entrainer in azeotrope tower so that the first tower underflow is separated at least the second tower top stream
With the second tower underflow, wherein said second tower top stream comprises alkyl acetate and water and wherein said second tower underflow comprises institute
State the first organic acid；
Organic facies and aqueous phase, described organic facies is become to comprise alkyl acetate described second tower top flow separation in phase separator；
And
Described organic facies returned to described azeotrope tower at least partially.
2. the method described in claim 1, the charging of wherein said hydrocarbon comprises propane.
3. the method described in claim 1, wherein said first organic acid is selected from acetic acid, propanoic acid, butanoic acid and any combination thereof.
4. the method described in claim 1, the charging of wherein said liquid waterborne also comprises the second organic acid, described second organic acid
Selected from acetic acid, propanoic acid, butanoic acid and any combination thereof, and wherein said second organic acid is different from described first organic acid.
5. the method described in claim 4, wherein said first tower underflow also comprises at least the 3rd organic acid.
6. the method described in claim 5, wherein said 3rd organic acid is selected from acetic acid, propanoic acid, butanoic acid and any combination thereof, and
And wherein said 3rd organic acid is different from described first organic acid and described second organic acid.
7. the method described in claim 1, wherein said first organic acid present in the second tower underflow concentration higher than the
Concentration in one tower underflow.
8. the method described in claim 1, it also includes the most described second tower underflow is returned to described reactor.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IN1329CH2011 | 2011-04-18 | ||
| IN1329/CHE/2011 | 2011-04-18 | ||
| PCT/US2012/032277 WO2012148643A1 (en) | 2011-04-18 | 2012-04-05 | Apparatus and process for nitration selectivity flexibility enabled by azeotropic distillation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103827076A CN103827076A (en) | 2014-05-28 |
| CN103827076B true CN103827076B (en) | 2016-11-30 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4476336A (en) * | 1983-07-05 | 1984-10-09 | W. R. Grace & Co. | Process for forming nitroparaffin |
| CN101854989A (en) * | 2007-07-18 | 2010-10-06 | 因维斯塔技术有限公司 | Azeotropic distillation for regeneration of entrainer |
| CN101998948A (en) * | 2008-04-16 | 2011-03-30 | 安格斯化学公司 | Nitrated hydrocarbons, derivatives, and processes for their manufacture |
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4476336A (en) * | 1983-07-05 | 1984-10-09 | W. R. Grace & Co. | Process for forming nitroparaffin |
| CN101854989A (en) * | 2007-07-18 | 2010-10-06 | 因维斯塔技术有限公司 | Azeotropic distillation for regeneration of entrainer |
| CN101998948A (en) * | 2008-04-16 | 2011-03-30 | 安格斯化学公司 | Nitrated hydrocarbons, derivatives, and processes for their manufacture |
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