CN107118106A - A kind of method that low-carbon alkanes prepare low-grade aliphatic amine through bromination ammonolysis - Google Patents
A kind of method that low-carbon alkanes prepare low-grade aliphatic amine through bromination ammonolysis Download PDFInfo
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Abstract
The present invention provides a kind of method that low-carbon alkanes prepare low-grade aliphatic amine through bromination ammonolysis, comprises the following steps：（1）Bromo-reaction：C1 C4 low-carbon alkanes unstripped gas is mixed with bromine gas, is catalyzed in bromination device through bromination catalyst, generation brominated alkanes, hydrogen bromide；（2）Ammonolysis reaction：By step（1）Product and ammoniacal liquor ammonolysis reaction occurs in liquid phase reactor tank, generate the aqueous solution and bromination aqueous ammonium of fat amine mixture, pass through ammoniacal liquor control system pH ＞ 8；（3）Separation：Bromination aqueous ammonium and unreacted low-carbon alkanes are separated；（4）Cell reaction：Bromination aqueous ammonium is pumped into diaphragm electrolysis apparatus, anode generation bromine, negative electrode generation ammoniacal liquor and hydrogen, bromine and ammoniacal liquor are recycled respectively, and hydrogen storage is standby.The low-carbon alkanes of low value can be converted into high value-added product low-grade aliphatic amine by this method, and method is simple, and cost is low, and the product prepared is easily separated, and purity is high.
Description
Technical field
The invention belongs to prepare the technical field of low-grade aliphatic amine, and in particular to a kind of low-carbon alkanes are through bromination-ammonolysis system
The method of standby low-grade aliphatic amine.
Background technology
Low-grade aliphatic amine is the important fine chemistry industry commodity and chemical industry base stock of a class, be widely used in oil field,
The industries such as petrochemical industry, synthetic material, weaving, medicine, agricultural chemicals.At present, the synthetic method of low-grade aliphatic amine mainly has three classes：Alcohol catalysis
Amination method, halogenated hydrocarbons ammonolysis process and nitrile or nitro compounds reducing process.The primary raw material of catalytic amination method is alcohol, and its accessory substance is
Water, production process is relatively cleaned, so, the low-grade aliphatic amine device such as domestic existing ethamine, propylamine, isopropylamine, butylamine always produces energy
The kt/a of power about 80, is substantially all the alcohol hydroamination technology path using advantage of lower cost, still, alcohol is still one now
The chemical products of class high added value, will expend substantial amounts of grain or cracking petrol gas, this personal value in current production process
Lattice are still costly；The raw material of halogenated hydrocarbons ammonolysis is halogenated hydrocarbons, caustic soda, ammonia, and it is tight that course of reaction adds caustic soda equipment corrosion
Weight, pollution is big, and by-product ammonium chloride and sodium chloride are more, it is impossible to recycle, and the cost of raw material is high and conversion ratio is low, product
Purity is low；In nitrile or nitro compounds reducing process, raw material and reducing agent price are higher, and the oxidation state of reducing agent is seriously polluted, are applicable model
Enclose narrow.As can be seen here, the high cost of raw material in the prior art, course of reaction equipment corrosion is serious, is produced in low-grade aliphatic amine
The problem of being one very big in journey, this considerably increases the cost of low-grade aliphatic amine.
In recent years, influenceed by the U.S. " revolution of shale oil gas ", and the continuous growth of natural gas proved reserves in recent years,
Natural gas is more and more paid attention to as a kind of important resource in fields such as the energy, chemical industry.By the lower alkanes of low value
Hydrocarbon, which is converted into the high added value chemicals such as lower aliphatic amine, obviously very big economic value.
The content of the invention
For the defect of prior art, the present invention provides one kind and low-carbon alkanes is prepared into rudimentary fat through bromination-ammonolysis
The method of fat amine, this method cost is low, energy-conserving and environment-protective, and obtained low-grade aliphatic amine purity is high.
A kind of method that low-carbon alkanes prepare low-grade aliphatic amine through bromination-ammonolysis, comprises the following steps：
（1）Bromo-reaction：C1-C4 low-carbon alkanes unstripped gas is mixed with bromine gas, urged in bromination device through bromination catalyst
Change, generation brominated alkanes, hydrogen bromide；
（2）Ammonolysis reaction：By step（1）Product and ammoniacal liquor ammonolysis reaction occurs in liquid phase reactor tank, generation fatty amine is mixed
The aqueous solution and bromination aqueous ammonium of compound, pass through ammoniacal liquor control system pH ＞ 8；
（3）Separation：Bromination aqueous ammonium and unreacted low-carbon alkanes are separated；
（4）Cell reaction：Bromination aqueous ammonium is pumped into diaphragm electrolysis apparatus, anode generation bromine, negative electrode generation ammoniacal liquor and hydrogen
Gas, bromine and ammoniacal liquor respectively enter step（1）And step（2）Recycled, hydrogen storage is standby.
Step（1）The bromination device is fixed bed reactors, and reaction temperature is 300-450 DEG C, and pressure is 0.1-1MPa,
Unstripped gas air speed 2000-10000h-1。
Step（1）Described in bromination catalyst be load type metal oxyhalide.
The load type metal oxyhalide is TaOF3/Al2O3、NbOF3/Al2O3、ZrOF2/Al2O3Or SbOF3/
Al2O3。
The load type metal oxyhalide can also be support type nonstoichiometric metal oxyhalide.
The support type nonstoichiometric metal oxyhalide is support type non-stoichiometric of the prior art gold
Belong to oxyhalide, such as Olah etc. is in J. Am. Chem. Soc. 1985, the FeO described in 107,7097-7105xBry/
Al2O3、FeOxCly/Al2O3,（Wherein, 2x+y=3, x ＞ 0, y ＞ 0）.
Step（1）Described in the volume ratio of low-carbon alkanes unstripped gas and bromine gas be（1-2）：（1-2）.
Step（1）Described in low-carbon alkanes unstripped gas come from natural gas or oven gas.
Step（2）In, the temperature of the ammonolysis reaction is 20-60 DEG C, pressure 0.1-1MPa.
Step（3）What is separated concretely comprises the following steps：By step（2）Product condensation, obtain gas-phase product and liquid product, gas
Phase product is unreacted low-carbon alkanes, and gas-phase product is passed through into step（1）Bromination device in；Liquid product extracting rectifying,
Using extractive distillation column, tower top regulation boiling range obtains each fatty amine product, and bottom of towe obtains ammonium bromide solution, i.e., by continuing essence
Evaporate, obtain fatty amine and bromination aqueous ammonium.
Step（4）Cell reaction：Bromination aqueous ammonium is pumped into diaphragm electrolysis apparatus, Br- is oxidized in anode region
Bromine simple substance is generated, step is pumped into by preheating gasification after bromine simple substance is separated（1）Bromination device in recycle；Cathodic region is passed through
Electrolysis obtains ammoniacal liquor and hydrogen, and ammoniacal liquor enters step（2）Ammonolysis device recycle, hydrogen as accessory substance store it is standby
With.
Step（4）In, in the diaphragm electrolysis apparatus, barrier film is one in ion exchange resin or cation-exchange membrane
Kind；Anode material is graphite or titanium；Cathode material is graphite or nickel.
Step（4）In, the condition of cell reaction is that voltage is 20-100V, current density 800-1600A/m2, temperature exists
30-70℃。
Advantages of the present invention：
（1）The unstripped gas low-carbon alkanes of low value can be converted into the rudimentary fat of high value-added product by the method that the present invention is provided
Fat amine, method is simple, and cost is low, and nonstaining property material is produced in course of reaction, environmental protection, to prepare low-grade aliphatic amine
There is provided a new approach；
（2）By bromo-reaction and ammonolysis reaction, the conversion per pass of unstripped gas is higher, and the product prepared is easily separated, pure
Degree is high；
（3）Isolated product is electrolysed, the equal reusable edible of bromine and ammoniacal liquor of generation can also produce the high hydrogen of added value
Gas, reduces reaction cost.
Brief description of the drawings
The flow chart of Fig. 1 embodiments 1
Wherein：1-unstripped gas CH4, 2-bromomethane, hydrogen bromide, 3-ammoniacal liquor, the aqueous solution and bromination of 4-methylamine mixture
Aqueous ammonium, 5-low-grade aliphatic amine rectifying product：Methylamine, 6-unreacted CH4, 7-bromination aqueous ammonium, 8-ammoniacal liquor, 9-
H2, 10-Br2, 11-fixed bed reactors (bromination device), 12-liquid phase reactor tank, 13-extractive distillation column, 14-barrier film electricity
Solve device.
Embodiment
Embodiment 1
1. a kind of method that low-carbon alkanes prepare low-grade aliphatic amine through bromination-ammonolysis（Schematic flow sheet is as shown in Figure 1）, including
Following steps：
（1）Bromo-reaction：By purity ＞ 90% CH4As unstripped gas, according to CH4, bromine gas volume ratio be 1：1, by CH4With bromine
Gas is mixed, in fixed bed reactors（Bromination device）Middle carry out bromo-reaction, wherein, load type gold is filled in fixed bed reactors
Belong to oxyhalide TaOF3/Al2O3, 450 DEG C of reaction temperature, pressure 0.5MPa, unstripped gas air speed 5000h-1, generation bromine first hydrocarbon, bromine
Change hydrogen；
（2）Ammonolysis reaction：By step（1）Product is pumped into liquid phase reactor tank, and ammoniacal liquor is filled with liquid phase reactor tank, passes through spray
EGR sprays the pH of ammonia spirit control system>8, the temperature of reaction is 20 DEG C, and pressure 1MPa generates fat amine mixture
The aqueous solution and bromination aqueous ammonium；
（3）Separation：By step（3）Product condensation, be cooled to -10 DEG C, gas-liquid separation obtains gas-phase product and liquid product, gas
Phase product is unreacted low-carbon alkanes, and gas-phase product is passed through into step（1）Bromination device in；Liquid product is in extracting rectifying
Extracting rectifying is carried out in tower, tower top regulation boiling range, -7 ~ -5 DEG C of cuts are monomethyl amine, 2 ~ 4 DEG C of cuts are trimethylamine, 6 ~ 9 DEG C of cuts
For dimethylamine.The bottom of extractive distillation column obtains ammonium bromide solution；
（4）Cell reaction：By step（3）Obtained ammonium bromide solution is pumped into diaphragm electrolysis apparatus, in electrolysis unit, and barrier film is
Ion exchange resin, anode material is graphite, and cathode material is nickel, and operating voltage is 20V, current density during cell reaction
800A/m2, electrolytic cell temperature is 30 DEG C, Br in anode region-Generation bromine simple substance is oxidized, by pre- hot gas after bromine simple substance is separated
Change is pumped into step（1）Fixed bed reactors in recycle；Cathodic region obtains ammoniacal liquor and hydrogen through electrolysis, and ammoniacal liquor enters step
Suddenly（2）Liquid-phase reactor in recycle, hydrogen is stored for future use as accessory substance.
After testing, unstripped gas CH4Conversion per pass 52%；Products obtained therefrom monomethyl amine purity>99%, dimethylamine purity>99%,
Trimethylamine purity>99%, byproduct H2Purity>99%.
Embodiment 2
1. a kind of method that low-carbon alkanes prepare low-grade aliphatic amine through bromination-ammonolysis, comprises the following steps：
（1）Bromo-reaction：By purity ＞ 95% C2H6As unstripped gas, according to C2H6, bromine gas volume ratio be 1：2, by C2H6With
Bromine gas is mixed, in fixed bed reactors（Bromination device）Middle carry out bromo-reaction, wherein, support type is filled in fixed bed reactors
Nonstoichiometric metal oxyhalide FeOxBry/Al2O3（Wherein, 2x+y=3, x ＞ 0, y ＞ 0）, 400 DEG C of reaction temperature, pressure
Power 0.1MPa, unstripped gas air speed 6000h-1, generation bromoethane, hydrogen bromide；
（2）Ammonolysis reaction：By step（1）Product is pumped into liquid phase reactor tank, and ammoniacal liquor is filled with liquid phase reactor tank, passes through spray
EGR sprays the pH of ammonia spirit control system>8, the temperature of reaction is 60 DEG C, pressure 0.1MPa, generation fatty amine mixing
The aqueous solution and bromination aqueous ammonium of thing；
（3）Separation：By step（3）Product condensation, be cooled to 0 DEG C, gas-liquid separation obtains gas-phase product and liquid product, gas phase
Product is unreacted low-carbon alkanes C2H6, gas-phase product is passed through step（1）Bromination device in；Liquid product is in extraction essence
Evaporate and extracting rectifying is carried out in tower, tower top regulation boiling range, 14 ~ 18 DEG C of cuts are monoethyl amine, 54 ~ 57 DEG C of cuts are diethylamine, 88 ~ 90
DEG C cut is triethylamine.The bottom of extractive distillation column obtains ammonium bromide solution；
（4）Cell reaction：By step（3）Obtained ammonium bromide solution is pumped into diaphragm electrolysis apparatus, in electrolysis unit, and barrier film is
Cation-exchange membrane, anode material is titanium, and cathode material is graphite, and operating voltage is 100V, current density during cell reaction
1600A/m2, electrolytic cell temperature is 70 DEG C, Br in anode region-Generation bromine simple substance is oxidized, by pre- hot gas after bromine simple substance is separated
Change is pumped into step（1）Fixed bed reactors in recycle；Cathodic region obtains ammoniacal liquor and hydrogen through electrolysis, and ammoniacal liquor enters step
Suddenly（2）Liquid-phase reactor in recycle, hydrogen is stored for future use as accessory substance.
After testing, unstripped gas C2H6Conversion per pass is 63%；Products obtained therefrom monoethyl amine purity>95%, diethylamine purity>
95%, triethylamine purity>95%, byproduct H2Purity>99%.
Embodiment 3
1. a kind of method that low-carbon alkanes prepare low-grade aliphatic amine through bromination-ammonolysis, comprises the following steps：
（1）Bromo-reaction：By purity ＞ 90% C3H8As unstripped gas, according to C3H8, bromine gas volume ratio be 2：1, by C3H8With
Bromine gas is mixed, in fixed bed reactors（Bromination device）Middle carry out bromo-reaction, wherein, support type is filled in fixed bed reactors
Metal oxyhalide ZrOF2/Al2O3, 300 DEG C of reaction temperature, pressure 1MPa, unstripped gas air speed 2000h-1, generation N-Propyl Bromide, bromine
Change hydrogen；
（2）Ammonolysis reaction：By step（1）Product is pumped into liquid phase reactor tank, and ammoniacal liquor is filled with liquid phase reactor tank, passes through spray
EGR sprays the pH of ammonia spirit control system>8, the temperature of reaction is 40 DEG C, pressure 0.5MPa, generation fatty amine mixing
The aqueous solution and bromination aqueous ammonium of thing；
（3）Separation：By step（3）Product condensation, be cooled to 0 DEG C, gas-liquid separation obtains gas-phase product and liquid product, gas phase
Product is unreacted low-carbon alkanes C3H8, gas-phase product is passed through step（1）Bromination device in；Liquid product is in extraction essence
Evaporate and extracting rectifying carried out in tower, tower top regulation boiling range, 32 ~ 35 DEG C of cuts are Mono Isopropylamine, 82 ~ 86 DEG C of cuts are diisopropylamine,
The bottom of extractive distillation column obtains ammonium bromide solution；
（4）Cell reaction：By step（3）Obtained ammonium bromide solution is pumped into diaphragm electrolysis apparatus, in electrolysis unit, and barrier film is
Cation-exchange membrane, anode material is titanium, and cathode material is graphite, and operating voltage is 40V, current density during cell reaction
1000A/m2, electrolytic cell temperature is 50 DEG C, Br in anode region-Generation bromine simple substance is oxidized, by pre- hot gas after bromine simple substance is separated
Change is pumped into step（1）Fixed bed reactors in recycle；Cathodic region obtains ammoniacal liquor and hydrogen through electrolysis, and ammoniacal liquor enters step
Suddenly（2）Liquid-phase reactor in recycle, hydrogen is stored for future use as accessory substance.
After testing, unstripped gas C3H8Conversion per pass is 67%；Products obtained therefrom Mono Isopropylamine purity>95%, diisopropylamine purity
>95%, byproduct H2Purity>99%.
Embodiment 4
1. a kind of method that low-carbon alkanes prepare low-grade aliphatic amine through bromination-ammonolysis, comprises the following steps：
（1）Bromo-reaction：By purity ＞ 90% C4H10As unstripped gas, according to C4H10, bromine gas volume ratio be 1.5：2, will
C4H10Mixed with bromine gas, in fixed bed reactors（Bromination device）Middle carry out bromo-reaction, wherein, filled in fixed bed reactors
Load type metal oxyhalide SbOF3/Al2O3, 450 DEG C of reaction temperature, pressure 0.5MPa, unstripped gas air speed 10000h-1, generation
NBB, hydrogen bromide；
（2）Ammonolysis reaction：By step（1）Product is pumped into liquid phase reactor tank, and ammoniacal liquor is filled with liquid phase reactor tank, passes through spray
EGR sprays the pH of ammonia spirit control system>8, the temperature of reaction is 50 DEG C, pressure 0.6MPa, generation fatty amine mixing
The aqueous solution and bromination aqueous ammonium of thing；
（3）Separation：By step（3）Product condensation, be cooled to 10 DEG C, gas-liquid separation obtains gas-phase product and liquid product, gas phase
Product is unreacted low-carbon alkanes C4H10, gas-phase product is passed through step（1）Bromination device in；Liquid product is in extraction essence
Evaporate and extracting rectifying is carried out in tower, tower top regulation boiling range, 44 ~ 46 DEG C of cuts are tert-butylamine, 62 ~ 64 DEG C of cuts are a sec-butylamine, 134
~ 138 DEG C of cuts are di-sec-butylamine, and the bottom of extractive distillation column obtains ammonium bromide solution；
（4）Cell reaction：By step（3）Obtained ammonium bromide solution is pumped into diaphragm electrolysis apparatus, in electrolysis unit, and barrier film is
Cation-exchange membrane, anode material is titanium, and cathode material is graphite, and operating voltage is 60V, current density during cell reaction
1200A/m2, electrolytic cell temperature is 50 DEG C, Br in anode region-Generation bromine simple substance is oxidized, by pre- hot gas after bromine simple substance is separated
Change is pumped into step（1）Fixed bed reactors in recycle；Cathodic region obtains ammoniacal liquor and hydrogen through electrolysis, and ammoniacal liquor enters step
Suddenly（2）Liquid-phase reactor in recycle, hydrogen is stored for future use as accessory substance.
After testing, unstripped gas C4H10Conversion per pass is 72%；Products obtained therefrom tert-butylamine purity>95%, a sec-butylamine purity>
95%, di-sec-butylamine purity>95%, byproduct H2Purity>99%.
As can be seen here, the low-carbon alkanes unstripped gas of low value, can be converted into high attached by the method provided using the present invention
Value added low-grade aliphatic amine, and product is single, easily separated, purity is high, and accessory substance can be recycled.
Claims (10)
1. a kind of method that low-carbon alkanes prepare low-grade aliphatic amine through bromination-ammonolysis, comprises the following steps：
（1）Bromo-reaction：C1-C4 low-carbon alkanes unstripped gas is mixed with bromine gas, urged in bromination device through bromination catalyst
Change, generation brominated alkanes, hydrogen bromide；
（2）Ammonolysis reaction：By step（1）Product and ammoniacal liquor ammonolysis reaction occurs in liquid phase reactor tank, generation fatty amine is mixed
The aqueous solution and bromination aqueous ammonium of compound, pass through ammoniacal liquor control system pH ＞ 8；
（3）Separation：Bromination aqueous ammonium and unreacted low-carbon alkanes are separated；
（4）Cell reaction：Bromination aqueous ammonium is pumped into diaphragm electrolysis apparatus, anode generation bromine, negative electrode generation ammoniacal liquor and hydrogen
Gas, bromine and ammoniacal liquor respectively enter step（1）And step（2）Recycled, hydrogen storage is standby.
2. the method that low-carbon alkanes prepare low-grade aliphatic amine through bromination-ammonolysis according to claim 1, it is characterised in that：Step
Suddenly（1）The bromination device is fixed bed reactors, and reaction temperature is 300-450 DEG C, and pressure is 0.1-1MPa, unstripped gas air speed
2000-10000h-1。
3. the method that low-carbon alkanes prepare low-grade aliphatic amine through bromination-ammonolysis according to claim 2, it is characterised in that：Institute
Bromination catalyst is stated for load type metal oxyhalide.
4. the method that low-carbon alkanes prepare low-grade aliphatic amine through bromination-ammonolysis according to claim 3, it is characterised in that：Institute
Bromination catalyst is stated for support type nonstoichiometric metal oxyhalide.
5. the method that low-carbon alkanes prepare low-grade aliphatic amine through bromination-ammonolysis according to claim 2, it is characterised in that：Institute
The volume ratio for stating low-carbon alkanes unstripped gas and bromine gas is（1-2）：（1-2）.
6. the method that the low-carbon alkanes according to claim 1 or 2 or 3 or 4 or 5 prepare low-grade aliphatic amine through bromination-ammonolysis, its
It is characterised by：The temperature of the ammonolysis reaction is 20-60 DEG C, pressure 0.1-1MPa.
7. the method that low-carbon alkanes prepare low-grade aliphatic amine through bromination-ammonolysis according to claim 1, it is characterised in that：Institute
State in diaphragm electrolysis apparatus, barrier film is one kind in ion exchange resin or cation-exchange membrane；Anode material is graphite or titanium；
Cathode material is graphite or nickel.
8. the method that the low-carbon alkanes according to claim 1 or 7 prepare low-grade aliphatic amine through bromination-ammonolysis, it is characterised in that：
The condition of cell reaction is that voltage is 20-100V, current density 800-1600A/m2, temperature is at 30-70 DEG C.
9. the method that the low-carbon alkanes according to claim 1 or 2 or 7 prepare low-grade aliphatic amine through bromination-ammonolysis, its feature exists
In：Step（3）What is separated concretely comprises the following steps：By step（2）Product condensation, obtain gas-phase product and liquid product, gas phase production
Thing is unreacted low-carbon alkanes, and gas-phase product is passed through into step（1）Bromination device in；Liquid product rectification, obtains fat
Amine and bromination aqueous ammonium.
10. the method that low-carbon alkanes prepare low-grade aliphatic amine through bromination-ammonolysis according to claim 6, it is characterised in that：Step
Suddenly（3）What is separated concretely comprises the following steps：By step（2）Product condensation, obtain gas-phase product and liquid product, gas-phase product is not
The low-carbon alkanes of reaction, step is passed through by gas-phase product（1）Bromination device in；Liquid product rectification, obtains fatty amine and bromine
Change aqueous ammonium.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109608329A (en) * | 2018-12-12 | 2019-04-12 | 浙江大学 | A kind of terephthalic acid production method of low bromine discharge |
| CN109622006A (en) * | 2018-11-30 | 2019-04-16 | 中国科学院山西煤炭化学研究所 | One kind lower fatty amine catalyst containing ammonia synthesis gas and preparation method thereof |
| CN112663078A (en) * | 2020-11-03 | 2021-04-16 | 重庆大学 | Device and method for preparing adiponitrile by electrolytic dimerization of acrylonitrile |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109622006A (en) * | 2018-11-30 | 2019-04-16 | 中国科学院山西煤炭化学研究所 | One kind lower fatty amine catalyst containing ammonia synthesis gas and preparation method thereof |
| CN109622006B (en) * | 2018-11-30 | 2021-11-12 | 中国科学院山西煤炭化学研究所 | Catalyst for preparing low-grade aliphatic amine from ammonia-containing synthesis gas and preparation method thereof |
| CN109608329A (en) * | 2018-12-12 | 2019-04-12 | 浙江大学 | A kind of terephthalic acid production method of low bromine discharge |
| CN112663078A (en) * | 2020-11-03 | 2021-04-16 | 重庆大学 | Device and method for preparing adiponitrile by electrolytic dimerization of acrylonitrile |
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