CN109096144A - A method of synthesis diethyl hydroxylamine - Google Patents
A method of synthesis diethyl hydroxylamine Download PDFInfo
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- CN109096144A CN109096144A CN201811173753.7A CN201811173753A CN109096144A CN 109096144 A CN109096144 A CN 109096144A CN 201811173753 A CN201811173753 A CN 201811173753A CN 109096144 A CN109096144 A CN 109096144A
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- 229920001174 Diethylhydroxylamine Polymers 0.000 title claims abstract description 35
- FVCOIAYSJZGECG-UHFFFAOYSA-N diethylhydroxylamine Chemical compound CCN(O)CC FVCOIAYSJZGECG-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 24
- 230000015572 biosynthetic process Effects 0.000 title description 7
- 238000003786 synthesis reaction Methods 0.000 title description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 72
- 239000003054 catalyst Substances 0.000 claims abstract description 41
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 238000005336 cracking Methods 0.000 claims abstract description 23
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000007864 aqueous solution Substances 0.000 claims abstract description 18
- 239000011964 heteropoly acid Substances 0.000 claims abstract description 16
- 239000011973 solid acid Substances 0.000 claims abstract description 14
- 230000002194 synthesizing effect Effects 0.000 claims abstract 2
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 claims description 33
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 33
- 238000002360 preparation method Methods 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 4
- 230000001476 alcoholic effect Effects 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims 2
- 238000002156 mixing Methods 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Natural products CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 22
- 238000007254 oxidation reaction Methods 0.000 description 11
- 239000007789 gas Substances 0.000 description 10
- 230000003647 oxidation Effects 0.000 description 10
- 239000007788 liquid Substances 0.000 description 9
- 238000004587 chromatography analysis Methods 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 8
- 238000004321 preservation Methods 0.000 description 8
- 229960000583 acetic acid Drugs 0.000 description 7
- 239000003377 acid catalyst Substances 0.000 description 7
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 6
- 229910004373 HOAc Inorganic materials 0.000 description 6
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 6
- 229910001882 dioxygen Inorganic materials 0.000 description 6
- 239000012362 glacial acetic acid Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000052 vinegar Substances 0.000 description 2
- 235000021419 vinegar Nutrition 0.000 description 2
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000005909 ethyl alcohol group Chemical group 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C239/00—Compounds containing nitrogen-to-halogen bonds; Hydroxylamino compounds or ethers or esters thereof
- C07C239/08—Hydroxylamino compounds or their ethers or esters
- C07C239/10—Hydroxylamino compounds or their ethers or esters having nitrogen atoms of hydroxylamino groups further bound to carbon atoms of unsubstituted hydrocarbon radicals or of hydrocarbon radicals substituted by halogen atoms or by nitro or nitroso groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/08—Ion-exchange resins
- B01J31/10—Ion-exchange resins sulfonated
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of methods for synthesizing diethyl hydroxylamine, comprising: (1) solid acid catalyst that load has heteropoly acid is packed into fixed bed reactors, control reaction bed temperature is 40 ~ 60 DEG C；(2) mixed aqueous solution of triethylamine, acetic acid and hydrogen peroxide is injected into the fixed bed reactors so that residence time of the mixed aqueous solution in the fixed bed reactors be 2 ~ for 24 hours；(3) product that the outlet of the fixed bed reactors obtains enters cracking reaction kettle, cracks up to product；The temperature of the cracking reaction kettle is 100 ~ 120 °C, pressure 600-700mmHg.The present invention can reduce the security risk in production process and product purity is higher, be it is a kind of meet diethyl hydroxylamine industrialization demand, the very strong new method of practicability.
Description
Technical field
The invention belongs to chemical fields, are related to a kind of production technology for preparing diethyl hydroxylamine.
Background technique
N, N- diethyl hydroxylamine (DEHA) sterling are colourless transparent liquid, and industrial goods are light yellow transparent liquid.It is relatively close
Spend 1.867 (0~20 DEG C), -25 DEG C of fusing point, 125~130 DEG C of boiling point, 45 DEG C of flash-point, refractive index 1.4195 (20 DEG C).DEHA is
A kind of novel high-efficiency polymerization inhibitor, its polymerization inhibitor is high-efficient, and inhibits efficiency and be not acted upon by temperature changes, it is not only in monomer
Liquid phase in have very high polymerization inhibitor efficiency, and in the gas phase also have good polymerization inhibition performance；And DEHA itself is nontoxic, and it is right
Product is pollution-free, and the solubility in monomer is big, and is easy to remove from monomer, easy to use.N, N- diethyl hydroxylamine
It is also the excellent terminator of polymerization reaction.
The synthetic method of N, N- diethyl hydroxylamine is relatively more.From the works such as synthesis cost, cost of material and yield, product purity
Industry angle is set out, and the synthesis most common two methods of DEHA are diethylamine oxidizing process and triethylamine oxicracking method.State at present
Inside and outside most of producers mainly use triethylamine oxicracking method to produce N, N- diethyl hydroxylamine, but pass through triethylamine and hydrogen peroxide
By oxidation, dehydration, cracking preparation N, it is more that the method for N- diethyl hydroxylamine is clearly present reaction step, and production technology is complicated, always
Yield is low, product purity is lower and is difficult to the disadvantages of removing product contained humidity completely, can especially generate in reaction a large amount of
The flammable explosive gas such as ethylene, to make in production process that there are some potential safety problemss.
Summary of the invention
In view of the above-mentioned problems, the present invention provides a kind of method using Peracetic acid into oxidative synthesis diethyl hydroxylamine.It should
Method, as catalyst, is carried out using Peracetic acid in a manner of continuous fixed bed reaction or continuous, prepares three second of oxidation by heterogeneous catalysis
Then amine obtains the diethyl hydroxylamine that yield is 80% or more by cracking reaction kettle and rectifying column.
The purpose of the present invention can be achieved through the following technical solutions:
A method of synthesis diethyl hydroxylamine, comprising the following steps:
(1) solid acid catalyst that load has heteropoly acid is packed into fixed bed reactors, control reaction bed temperature is
40~60 DEG C；
(2) mixed aqueous solution of triethylamine, acetic acid and hydrogen peroxide is injected into the fixed bed reactors, so that described mixed
Residence time of the Heshui solution in the fixed bed reactors be 2~for 24 hours；
(3) product that the outlet of the fixed bed reactors obtains enters cracking reaction kettle, cracks up to product；It is described to split
The temperature of solution reaction kettle is 100~120 DEG C, and pressure is 600~700mmHg.
Further, the preferred temperature of step (1) is 50~60 DEG C.
Further, heteropoly acid described in step (1) is phosphotungstic acid.
Further, solid acid catalyst described in step (1) is Amberlyst-15.
Further, load described in step (1) has the solid acid catalyst of heteropoly acid, and catalyst supported quantity is 10~
30%wt；The additional amount that the load has the solid acid catalyst of heteropoly acid is the 2~10% of total reactant quality.Supported quantity
It is calculated according to immobilized the of poor quality of front and back solid acid catalyst.
Further, load described in step (1) has the solid acid catalyst of heteropoly acid, and preparation method includes:
Solid acid catalyst is immersed in 3~4h in alcoholic solvent, is dried to weight later, the water-soluble of heteropoly acid is then added
Liquid stir 4~6h, be washed to neutrality later, be dried to weight to get.
Preferably, the alcoholic solvent is ethyl alcohol.
Preferably, the drying is in 30~40 DEG C of drying
Preferably, the aqueous solution of the heteropoly acid, concentration are 1~5%wt.
Further, in step (2), triethylamine, hydrogen peroxide, acetic acid the mass ratio of the material are 1:1~1.1:1~2.
Further, the preferred temperature of step (3) is 105~110 DEG C.
Further, the preferred pressure of step (3) is 660~680mmHg.
The oxidization time that the present invention reacts be 2~for 24 hours.
The beneficial effects of the present invention are:
Solid-carrying heteropolyacid catalyst activity is big, selective high in the present invention, and may be reused.Pass through hydrogen peroxide and vinegar
The product Peracetic acid of acid is as oxidizing synthesis diethyl hydroxylamine, compared with traditional oxidant hydrogen peroxide, diethyl
The yield of azanol is higher, purity is more excellent and reduces the security risk of the product ethylene in cracking process.
Specific embodiment
Embodiment 1
(1) catalyst preparation of Amberlyst-15 immobilized phosphotungstic acid:
Amberlyst-15 is immersed in ethanol solution first, stirring 3h under room temperature is later 40 DEG C of items in temperature
It is spare that weight is dried under part.Phosphotungstic acid (the H for being 1.0% by mass concentration3PW12O40·XH2O) aqueous solution is added at 50.0g
In the Amberlyst-15 managed, 6h is stirred at room temperature, neutrality is washed to after stirring, 40 DEG C are dried to weight, obtain
Amberlyst-15 immobilized phosphotungstic acid catalyst 58.4g (supported quantity 14.25%).
(2) preparation of diethyl hydroxylamine:
The catalyst of 9.5gAmberlyst-15 immobilized phosphotungstic acid is taken to be packed into fixed bed reactors, catalyst bed heat preservation exists
60℃.By 101.2g (1.00mol) triethylamine (DEA) and 200g (11.11mol) water, 60.06g (1.00mol) glacial acetic acid
(HOAc) and the dioxygen water mixed liquid of 113.36g (1.00mol) 30% is with constant speed injection reactor, in reactor after stopping for 24 hours
Outlet obtains oxidation triethylamine and enters cracking reaction kettle and rectifying column, and the temperature of cracking reaction is 110 DEG C, pressure 660.?
To target product diethyl hydroxylamine yield 85.87%, gas chromatographic analysis pure 94.5%.
Embodiment 2
(1) catalyst preparation of Amberlyst-15 immobilized phosphotungstic acid:
Amberlyst-15 is immersed in ethanol solution first, stirring 4h under room temperature is later 40 DEG C of items in temperature
It is spare that weight is dried under part.Phosphotungstic acid (the H for being 2.0% by mass concentration3PW12O40·XH2O) aqueous solution is added at 50.0g
In the Amberlyst-15 managed, 4h is stirred at room temperature, neutrality is washed to after stirring, 40 DEG C are dried to weight, obtain
Amberlyst-15 immobilized phosphotungstic acid catalyst 61.41g (supported quantity 18.57%).
(2) preparation of diethyl hydroxylamine:
The catalyst of 49gAmberlyst-15 immobilized phosphotungstic acid is taken to be packed into fixed bed reactors, catalyst bed heat preservation exists
50℃.By 101.2g (1.00mol) triethylamine (DEA) and 200g (11.11mol) water, 66.06g (1.1mol) glacial acetic acid
(HOAc) and the mixed liquor of the hydrogen peroxide of 124.7g (1.1mol) 30% is with constant speed injection reactor, stops after 12h in reactor
Outlet obtains oxidation triethylamine and enters cracking reaction kettle and rectifying column, and the temperature of cracking reaction is 105 DEG C, and pressure is
680mmHg.Obtain target product diethyl hydroxylamine yield 86.09%, gas chromatographic analysis pure 94.7%.
Embodiment 3
(1) catalyst preparation of Amberlyst-15 immobilized phosphotungstic acid:
Amberlyst-15 is immersed in ethanol solution first, stirring 4h under room temperature is later 40 DEG C of items in temperature
It is spare that weight is dried under part.Phosphotungstic acid (the H for being 3.0% by mass concentration3PW12O40·XH2O) aqueous solution is added at 50.0g
In the Amberlyst-15 managed, 4h is stirred at room temperature, neutrality is washed to after stirring, 40 DEG C are dried to weight, obtain
Amberlyst-15 immobilized phosphotungstic acid catalyst 64.57g (supported quantity 22.57%).
(2) preparation of diethyl hydroxylamine:
The catalyst of 20gAmberlyst-15 immobilized phosphotungstic acid is taken to be packed into fixed bed reactors, catalyst bed heat preservation exists
40℃.By 101.2g (1.00mol) triethylamine (DEA) and 100g (11.11mol) water, 90.08g (1.5mol) glacial acetic acid
(HOAc) and the dioxygen water mixed liquid of 113.36g (1.0mol) 30% is with constant speed injection reactor, goes out after stopping 2h in reactor
Mouth obtains oxidation triethylamine and enters cracking reaction kettle and rectifying column, and the temperature of cracking reaction is 120 DEG C, pressure 600mmHg.
Obtain target product diethyl hydroxylamine yield 89.01%, gas chromatographic analysis pure 94.5%.
Embodiment 4
(1) catalyst preparation of Amberlyst-15 immobilized phosphotungstic acid:
Amberlyst-15 is immersed in ethanol solution first, stirring 4h under room temperature is later 40 DEG C of items in temperature
It is spare that weight is dried under part.Phosphotungstic acid (the H for being 4.0% by mass concentration3PW12O40·XH2O) aqueous solution is added at 50.0g
In the Amberlyst-15 managed, 4h is stirred at room temperature, neutrality is washed to after stirring, 40 DEG C are dried to weight, obtain
Amberlyst-15 immobilized phosphotungstic acid catalyst 62.33g (supported quantity 19.78%).
(2) preparation of diethyl hydroxylamine:
The catalyst of 42gAmberlyst-15 immobilized phosphotungstic acid is taken to be packed into fixed bed reactors, catalyst bed heat preservation exists
55℃.By 101.2g (1.00mol) triethylamine (DEA) and 200g (11.11mol) water, 99.08g (1.65mol) glacial acetic acid
(HOAc) and the dioxygen water mixed liquid of 124.7g (1.1mol) 30% is with constant speed injection reactor, stops after 6h in reactor outlet
It obtains oxidation triethylamine and enters cracking reaction kettle and rectifying column, the temperature of cracking reaction is 100 DEG C, pressure 700mmHg.?
To target product diethyl hydroxylamine yield 87.03%, gas chromatographic analysis pure 95.1%.
Embodiment 5
(1) catalyst preparation of Amberlyst-15 immobilized phosphotungstic acid:
Amberlyst-15 is immersed in ethanol solution first, stirring 4h under room temperature is later 30 DEG C of items in temperature
It is spare that weight is dried under part.Phosphotungstic acid (the H for being 5.0% by mass concentration3PW12O40·XH2O) aqueous solution is added at 50.0g
In the Amberlyst-15 managed, 4h is stirred at room temperature, neutrality is washed to after stirring, 30 DEG C are dried to weight, obtain
Amberlyst-15 immobilized phosphotungstic acid catalyst 67.18g (supported quantity 25.57%).
(2) preparation of diethyl hydroxylamine:
The catalyst of 21.4gAmberlyst-15 immobilized phosphotungstic acid is taken to be packed into fixed bed reactors, catalyst bed heat preservation
At 45 DEG C, preferably 55~60 DEG C.By 101.2g (1.00mol) triethylamine (DEA) and 200g (11.11mol) aqueous solution, 120.1g
The dioxygen water mixed liquid of (2.00mol) glacial acetic acid (HOAc) and 113.36g (1.00mol) 30% inject reactor with constant speed, stop
It stays and obtains oxidation triethylamine in reactor outlet after 18h and enter cracking reaction kettle and rectifying column, the temperature of cracking reaction is 115
DEG C, pressure 640mmHg.Obtain target product diethyl hydroxylamine yield 88.79%, gas chromatographic analysis pure 94.5%.
Embodiment 6
(1) catalyst preparation of Amberlyst-15 immobilized phosphotungstic acid:
Amberlyst-15 is immersed in ethanol solution first, stirring 3h under room temperature is later 40 DEG C of items in temperature
It is spare that weight is dried under part.Phosphotungstic acid (the H for being 2.5% by mass concentration3PW12O40·XH2O) aqueous solution is added at 50.0g
In the Amberlyst-15 managed, 4h is stirred at room temperature, neutrality is washed to after stirring, 40 DEG C are dried to weight, obtain
Amberlyst-15 immobilized phosphotungstic acid catalyst 55.4g (supported quantity 10%).
(2) preparation of diethyl hydroxylamine:
The catalyst of 10.7gAmberlyst-15 immobilized phosphotungstic acid is taken to be packed into fixed bed reactors, catalyst bed heat preservation
At 60 DEG C.By 101.2g (1.00mol) triethylamine (DEA) and 200g (11.11mol) aqueous solution, 120.1g (2.00mol) ice vinegar
The dioxygen water mixed liquid of sour (HOAc) and 113.36g (1.00mol) 30% inject reactor with constant speed, in reaction after stopping for 24 hours
Device exports to obtain oxidation triethylamine and enters cracking reaction kettle and rectifying column, and the temperature of cracking reaction is 120 DEG C, and pressure is
680mmHg.Obtain target product diethyl hydroxylamine yield 89.79%, gas chromatographic analysis pure 94.1%.
7 comparative example of embodiment
(1) catalyst preparation of Amberlyst-15 immobilized phosphotungstic acid:
Amberlyst-15 is immersed in ethanol solution first, stirring 3h under room temperature is later 40 DEG C of items in temperature
It is spare that weight is dried under part.Phosphotungstic acid (the H for being 5% by mass concentration3PW12O40·XH2O) aqueous solution is added to 50.0g processing
In the Amberlyst-15 crossed, 6h is stirred at room temperature, neutrality is washed to after stirring, 40 DEG C are dried to weight, obtain Amberlyst-
15 immobilized phosphotungstic acid catalyst 71.5g (supported quantity 30%).
(2) preparation of diethyl hydroxylamine:
The catalyst of 10.7gAmberlyst-15 immobilized phosphotungstic acid is taken to be packed into fixed bed reactors, catalyst bed heat preservation
At 60 DEG C.By 101.2g (1.00mol) triethylamine (DEA), 200g (11.11mol) aqueous solution and 113.36g (1.00mol)
30% dioxygen water mixed liquid injects reactor with constant speed, obtains oxidation triethylamine entrance in reactor outlet after stopping for 24 hours and splits
Solution reaction kettle and rectifying column, the temperature of cracking reaction are 120 DEG C, pressure 680mmHg.Obtain target product diethyl hydroxylamine
Yield 75.79%, gas chromatographic analysis pure 94.3%.
8 comparative example of embodiment
(1) catalyst preparation of Amberlyst-15 immobilized phosphotungstic acid:
Take the catalyst 15g for the Amberlyst-15 immobilized phosphotungstic acid being prepared according to embodiment 5 (1)
(2) preparation of diethyl hydroxylamine:
The catalyst of the Amberlyst-15 immobilized phosphotungstic acid of 15g is packed into fixed bed reactors, catalyst bed heat preservation
At 60 DEG C.By 101.2g (1.00mol) triethylamine (DEA), 200g (11.11mol) aqueous solution and 103g (2.00mol) peroxide second
Sour mixed liquor with constant speed inject reactor, stop 10h after in reactor outlet obtain oxidation triethylamine enter cracking reaction kettle with
And rectifying column, the temperature of cracking reaction are 120 DEG C, pressure 680mmHg.Obtain target product diethyl hydroxylamine yield
88.21%, gas chromatographic analysis pure 94.2%.
Claims (10)
1. a kind of method for synthesizing diethyl hydroxylamine, which comprises the following steps:
(1) solid acid catalyst that load has heteropoly acid is packed into fixed bed reactors, control reaction bed temperature is 40 ~ 60
℃；It is preferred that 50 ~ 60 DEG C；
(2) mixed aqueous solution of triethylamine, acetic acid and hydrogen peroxide is injected into the fixed bed reactors, so that the mixing water
Residence time of the solution in the fixed bed reactors be 2 ~ for 24 hours；
(3) product that the outlet of the fixed bed reactors obtains enters cracking reaction kettle, cracks up to product；The cracking is anti-
The temperature for answering kettle is 100 ~ 120 °C, and pressure is 600 ~ 700mmHg.
2. the method according to claim 1, wherein heteropoly acid described in step (1) is phosphotungstic acid.
3. the method according to claim 1, wherein solid acid catalyst described in step (1) is
Amberlyst-15。
4. the method according to claim 1, wherein load described in step (1) has the solid acid of heteropoly acid to urge
Agent, catalyst supported quantity are 10 ~ 30%wt；The additional amount that the load has the solid acid catalyst of heteropoly acid is total anti-
Answer the 2 ~ 10% of amount of substance.
5. the method according to claim 1, wherein load described in step (1) has the solid acid of heteropoly acid to urge
Agent, preparation method include:
Solid acid catalyst is immersed in 3 ~ 4h in alcoholic solvent, is dried to weight later, the aqueous solution that heteropoly acid is then added stirs
Mix 4 ~ 6h, be washed to neutrality later, be dried to weight to get.
6. according to the method described in claim 5, it is characterized in that, the drying is in 30 ~ 40 DEG C of drying.
7. according to the method described in claim 5, it is characterized in that, the aqueous solution of the heteropoly acid, concentration are 1 ~ 5%wt.
8. the method according to claim 1, wherein in step (2), the amount of triethylamine, hydrogen peroxide, acetic acid substance
Than for 1:1 ~ 1.1:1 ~ 2.
9. the method according to claim 1, wherein the temperature of step (3) is 105 ~ 110 DEG C.
10. the method according to claim 1, wherein the pressure of step (3) is 660 ~ 680mmHg.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112300025A (en) * | 2020-11-03 | 2021-02-02 | 中触媒新材料股份有限公司 | Method for synthesizing N, N-diethylhydroxylamine by using fixed bed |
| CN112375011A (en) * | 2020-11-03 | 2021-02-19 | 济宁康德瑞化工科技有限公司 | Preparation method of N, N-diethylhydroxylamine |
| CN112591721A (en) * | 2021-01-05 | 2021-04-02 | 浙江锦华新材料股份有限公司 | Preparation method of solid hydroxylamine sulfate |
| CN113135837A (en) * | 2020-01-18 | 2021-07-20 | 济宁康德瑞化工科技有限公司 | Treatment system of triethylamine oxide cracking process tail gas |
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| CN112300025A (en) * | 2020-11-03 | 2021-02-02 | 中触媒新材料股份有限公司 | Method for synthesizing N, N-diethylhydroxylamine by using fixed bed |
| CN112375011A (en) * | 2020-11-03 | 2021-02-19 | 济宁康德瑞化工科技有限公司 | Preparation method of N, N-diethylhydroxylamine |
| CN112591721A (en) * | 2021-01-05 | 2021-04-02 | 浙江锦华新材料股份有限公司 | Preparation method of solid hydroxylamine sulfate |
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