CN1178885C - Method for preparing 1,3-propylene glycol - Google Patents

Abstract

The present invention relates to a preparation method of 1, 3-propanediol, which comprises the following steps: (1), reacting formaldehyde and acetaldehyde under the condition of the existence of alkali and an organic solvent for 2 to 10 hours at 10 to 40DEGC to generate 3-hydroxy propylaldehyde; (2), contacting the 3-hydroxy propylaldehyde and an alloy catalyst to carry out hydrogenation reaction under the conditions of 50 to 100 DEG C and 3 to 9MPa. The alloy catalyst comprises the following components by weight: 70 to 90 % of nickel, 0 to 9 % of iron or molybdenum, 1 to 5 % of phosphorus and aluminum as the rest. The preparation method of the present invention has the characteristics of low raw material price, good security and mild reaction condition. The alloy catalyst has the advantages of high activity and high selectivity; the yield of the 1, 3-propanediol can reach 90 mol%; the alloy catalyst can be reused, and thus, the production cost is reduced; simultaneously, inorganic by-products, such as Al(OH)3, etc., can not be generated.

Description

1, the preparation method of ammediol

Technical field

The present invention relates to 1, the preparation method of ammediol

Background technology

1, ammediol is important Organic Chemicals, is mainly used in the production polymkeric substance, and as thermoplastic polyurethane, poly terephthalic acid 1, ammediol ester (PTT), copolyester ether etc. also can be used as solvent, antifreezing agent and protective material.Wherein, replace 1 with it, 4-butyleneglycol, the prepared PTT performance of ethylene glycol are better than PBT (poly terephthalic acid 1,4-butanediol ester) and PET (polyethylene terephthalate).

In the prior art 1, the preparation method of ammediol mainly contains following two kinds of routes:

(1) be raw material with oxyethane, through hydroformylation, repeated hydrogenation preparation 1, ammediol.For example to adopt the promoted cobalt-carbonyl of rhodium carbonyls be hydroformylation catalyst for US 5689016, is hydrogenation catalyst with Ni, Co, Ru, Pt, Pd, must control 3-hydroxy propanal in the product of hydroformylation concentration＜15%, preferably be controlled at 5～10%.

The 2 ethyl hexanoic acid cobalt that US 5304686 adopts the di-t-butyl modification is as hydroformylation catalyst, and the acetic acid erbium is an auxiliary agent, and hydrogenation catalyst is Raney Ni, and hydrogenating materials needs the 3-hydroxy propanal is diluted to 3～20%, is preferably 3～5%.

The subject matter that above-mentioned technology exists is that high feed stock conversion and target product selectivity can't eat one's cake and have it, 1, and the ammediol once through yield as increasing yield, must use expensive rhodium carbonyl Rh all less than 75% ₄(CO) ₁₂Deng as auxiliary agent, hydroformylation needs carry out under the 100atm high pressure, and oxyethane is inflammable and explosive, react wayward, and is greatly dangerous.Hydroformylation reaction and hydrogenation reaction all need product and concentration of reactants are controlled at very low level, make that the service efficiency of reactor declines to a great extent in the two-step reaction.

(2) with the propenal be raw material, through hydration, hydrogenation preparing 1, ammediol.It is the phosphoric acid catalyst of carrier that EP 544120 adopts titanium dioxide, and the acrolein hydration after the dilution is become the 3-hydroxy propanal, with 3-hydroxy propanal hydrogenation under the effect of Raney Ni catalyzer, makes 1, ammediol again.

Above-mentioned route also exists and first kind of route similar problem, and 1, the once through yield of ammediol is lower, in hydration and the hydrogenation two-step reaction, all need control product and concentration of reactants, and the service efficiency of reactor is declined to a great extent.In addition, propenal is inflammable, extremely the poison and have the height pungency, price is expensive.

Summary of the invention

The objective of the invention is to overcome above-mentioned defective, is raw material with safety and formaldehyde, acetaldehyde cheap and easy to get, prepares 1, ammediol under than the demulcent condition.

Provided by the invention 1, the preparation method of ammediol comprises:

(1) formaldehyde, acetaldehyde are reacted generation 3-hydroxy propanal in the presence of alkali and organic solvent.Specifically, formaldehyde, acetaldehyde, alkali and organic solvent are mixed, at 10～40 ℃, preferred 15～30 ℃, reacted 2～10 hours, preferred 2～4 hours, product can obtain the 3-hydroxy propanal through distillation.It is excessive 5～30% that wherein acetaldehyde cans be compared to most formaldehyde, and simultaneously in order to improve the selectivity of 3-hydroxy propanal, the mode that reactant is preferably taked to drip is mixed.Used alkali is sodium hydroxide, potassium hydroxide or deacidite.The mol ratio of alkali and formaldehyde is 0.007～1: 1, preferred 0.01～0.05: 1.Said organic solvent can be aromatic hydrocarbons, haloalkane or low-carbon alcohol, as toluene, dimethylbenzene, trichloromethane and isooctyl alcohol etc.

(2) the 3-hydroxy propanal is contacted with alloy catalyst carry out hydrogenation reaction, generate 1, ammediol.Said catalyzer consists of: the heavy % of nickel 70～90, and preferred 75～85 heavy %, iron or molybdenum 0～9 heavy %, preferred 0～5 heavy %, phosphorus 1～5 heavy %, preferred 1～3%, surplus is an aluminium.The hydrogenation technique condition is: 50～100 ℃ of temperature, preferred 50～80 ℃, pressure 3～9MPa, preferred 6～7MPa.Reaction can be carried out in stirring tank or fixed bed.

Said alloy catalyst adopts following method preparation:

1) preparation Ni-P mother alloy will add in the quantitative phosphorus after the quantitative nickel fusion, and the two is alloying voluntarily, and the consumption of phosphorus is 15～30 heavy % of nickel, phosphorus total amount;

2) in the Ni-P mother alloy, add quantitative iron and aluminium or molybdenum and aluminium, in vacuum smelting furnace, refine into Ni-Fe-P-Al alloy or Ni-Mo-P-Al alloy, the consumption of iron or molybdenum is 0.5～15 heavy % of Ni-Fe-P-Al alloy or Ni-Mo-P-Al alloy, and the consumption of aluminium is 40～60 heavy % of Ni-Fe-P-Al alloy or Ni-Mo-P-Al alloy;

3) with vacuum quench (open clear 61-212332 referring to the spy and reach wherein Fig. 2) fast quenching Ni-Fe-P-Al alloy or Ni-Mo-P-Al alloy, the fast quenching condition is copper roller linear velocity 20～40 meter per seconds, spraying pressure 0.05～0.1MPa, 1200～1500 ℃ of injection temperatures;

4) with 3) product that obtains places the ventilated environment efflorescence to maximum particle size 300～500 orders;

5) with 4) alloy after the efflorescence that obtains places the aqueous sodium hydroxide solution of 10～25 heavy % to stir 0.5～5 hour in 0～50 ℃, preferably stirred 10 minutes to 1.5 hours at 0 ℃ earlier, stirred 0.5～4 hour in 30～50 ℃ again, to neutral, promptly get described catalyzer with the deionized water wash solid product.Wherein sodium hydroxide concentration is advisable with (with respect to Al content in the alloy) more than the excessive 30 heavy %.Show through material phase analysis: nickel is to exist with the excessive attitude form between crystalline state or non-crystalline state and crystalline state and the non-crystalline state in this catalyzer.

The inventive method has following characteristics:

(1) propenal and oxyethane are as the operational path of raw material relatively, and acetaldehyde, formaldehyde that the inventive method adopts have the advantages that price is low, security is good.

(2) whole technological reaction pressure is lower, even pressure is lower than 7MPa in the step, still can obtain good effect (2).

(3) the alloy hydrogenation catalyzer of employing high reactivity, highly selective makes 1, and the ammediol yield can reach 90mol%, and catalyzer is reusable, has reduced production cost, simultaneously also can be because of adopting aluminum isopropylate as the hydrogenating reduction agent, and the unit consumption of catalyzer is increased, and produce Al (OH) ₃Etc. inorganic byproduct.

Embodiment

Embodiment 1

Present embodiment is the preparation of catalyst A.

(1) put into 20 phosphorus (technical pure) that restrain in crucible, will pour in the crucible that phosphorus is housed after nickel (technical pure) fusions of 80 grams, nickel phosphorus is alloying voluntarily, gets the Ni-P mother alloy after the cooling.

(2) add 1 gram molybdenum and 50 gram aluminium (technical pure) in 49 gram Ni-P mother alloys, place vacuum button stove then, treat to keep 20 minutes after its fusion, vacuum tightness is 10 in stove ^-2Torr, 1200 ℃ of temperature charge into argon gas to normal pressure, make the Ni-Mo-P-Al alloy.

(3) obtain the Ni-Mo-P-Al alloy with vacuum quench fast quenching, the fast quenching condition is copper roller linear velocity 39 meter per seconds, spraying pressure 0.09MPa, 1260 ℃ of injection temperatures;

(4) be 300 orders with product efflorescence to the largest particle in ventilated environment that makes.

(5) the Ni-Mo-P-Al Ni-P that (4) are obtained places the aqueous sodium hydroxide solution of 22 heavy %, stirs 10 minutes at 0 ℃, in 40 ℃ of stirrings 40 minutes, to neutral, promptly gets described catalyst A with the deionized water wash solid product again.The weight of catalyst A is composed as follows: Ni 83%, and Mo 1.5%, and P 1.8%, and Al 13.7%.

Embodiment 2

Present embodiment is the preparation of catalyst B.

(1) put into 20 phosphorus (technical pure) that restrain in crucible, will pour in the crucible that phosphorus is housed after nickel (technical pure) fusions of 80 grams, nickel phosphorus is alloying voluntarily, gets the Ni-P mother alloy after the cooling.

(2) add 2 gram iron and 50 gram aluminium (technical pure) in 48 gram Ni-P mother alloys, place vacuum button stove then, treat to keep 20 minutes after its fusion, vacuum tightness is 10 in stove ^-2Torr, 1200 ℃ of temperature charge into argon gas to normal pressure, make the Ni-Fe-P-Al alloy.

(3) Ni-Fe-P-Al alloy or the Ni-Mo-P-Al alloy that obtains with vacuum quench fast quenching, fast quenching condition are copper roller linear velocity 39 meter per seconds, spraying pressure 0.09MPa, 1260 ℃ of injection temperatures;

(4) be 300 orders with product efflorescence to the largest particle in ventilated environment that makes.

(5) the Ni-Fe-P-Al alloy that (4) are obtained places the aqueous sodium hydroxide solution of 17 heavy %, stirred 10 minutes at 0 ℃, stirred 1.5 hours in 40 ℃ again, extremely neutral with the deionized water wash solid product, promptly get described catalyst B, its weight consists of: Ni 75.9%, and Fe 4.9%, P 2.8%, and Al 16.4%.

Embodiment 3

Dissolve trioxymethylene 1.0mol (in formaldehyde) as solution A with the 100ml isooctyl alcohol, with equivalent dimethylbenzene from concentration be the acetaldehyde solution of 40wt% extraction 1.06mol acetaldehyde as solution B, add the 100ml isooctyl alcohol at the 1L there-necked flask, 0.44gKOH is at 15 ± 2 ℃, normal pressure stirs down, with A, B splashes into wherein simultaneously, drips off the back restir, coreaction 2.5 hours, reaction product obtains the 3-hydroxy propanal after underpressure distillation.

In being the autoclave of 0.5L, loading amount adds 300ml, 23% the 3-hydroxy propanal aqueous solution, and the catalyst B add-on is 5 grams, at 60 ± 2 ℃, 6.9MPa reacts under the condition of mixing speed 1000rpm, products therefrom by analysis after as can be known, the yield of 1,3 propylene glycol is 90mol%.

Embodiment 4

Dissolve 0.8mol trioxymethylene (in formaldehyde) as solution A with the 100ml isooctyl alcohol, dissolve 1mol acetaldehyde as solution B with the equivalent isooctyl alcohol, add the 100ml isooctyl alcohol at the 1L there-necked flask, 1.0gNaOH is at 40 ± 2 ℃, normal pressure stirs down, with A, the B constant speed splashes into wherein, drips off the back restir, coreaction 2.5 hours, reaction product obtains the 3-hydroxy propanal after underpressure distillation.

In being the autoclave of 0.5L, loading amount adds 300ml, 31% the 3-hydroxy propanal aqueous solution, and the catalyst A add-on is 2.5 grams, at 70 ± 5 ℃, 5 ± 0.2MPa reacts under the condition of mixing speed 1000rpm, products therefrom by analysis after as can be known, the yield of 1,3 propylene glycol is 82mol%.

Claims (9)

1. one kind 1, the preparation method of ammediol comprises:

(1) with formaldehyde, acetaldehyde in the presence of alkali and organic solvent, 10～40 ℃ of reactions 2～10 hours, generate the 3-hydroxy propanal, used alkali is sodium hydroxide, potassium hydroxide or deacidite;

(2) the 3-hydroxy propanal is contacted with alloy catalyst, at 50～100 ℃, carry out hydrogenation reaction under the condition of 3～9MPa, said catalyzer consists of: nickel 70～90 heavy %, and iron or molybdenum 0～9 heavy %, phosphorus 1～5 heavy %, surplus is an aluminium.

2. according to the described preparation method of claim 1, it is characterized in that (1) step was 15～30 ℃ of reactions 2～4 hours.

3. according to the described preparation method of claim 1, it is characterized in that acetaldehyde is than the excessive 5～30mol% of formaldehyde, the mol ratio of alkali and formaldehyde is 0.007～1: 1.

4. according to the described preparation method of claim 3, it is characterized in that the mol ratio of alkali and formaldehyde is 0.01～0.05: 1.

5. according to the described preparation method of claim 1, it is characterized in that said organic solvent is aromatic hydrocarbons, haloalkane or isooctyl alcohol.

6. according to the described preparation method of claim 5, it is characterized in that said organic solvent is selected from toluene, dimethylbenzene, trichloromethane and isooctyl alcohol.

7. according to the described preparation method of claim 1, it is characterized in that hydroconversion condition is 50～80 ℃ of temperature, pressure 6～7MPa.

8. according to the described preparation method of claim 1, it is characterized in that catalyzer consists of: nickel 75～85 heavy %, iron or molybdenum 0～5 heavy %, phosphorus 1～3%, surplus is an aluminium.

9. according to the described preparation method of claim 1, it is characterized in that said alloy catalyst adopts following method preparation:

1) preparation Ni-P mother alloy will add in the quantitative phosphorus after the quantitative nickel fusion, and the two is alloying voluntarily, and the consumption of phosphorus is 15～30 heavy % of nickel, phosphorus total amount;

2) in the Ni-P mother alloy, add quantitative iron and aluminium or molybdenum and aluminium, in vacuum smelting furnace, refine into Ni-Fe-P-Al alloy or Ni-Mo-P-Al alloy, the consumption of iron or molybdenum is 0.5～15 heavy % of Ni-Fe-P-Al alloy or Ni-Mo-P-Al alloy, and the consumption of aluminium is 40～60 heavy % of Ni-Fe-P-Al alloy or Ni-Mo-P-Al alloy;

3) with vacuum quench fast quenching Ni-Fe-P-Al alloy or Ni-Mo-P-Al alloy, the fast quenching condition is copper roller linear velocity 20～40 meter per seconds, spraying pressure 0.05～0.1MPa, 1200～1500 ℃ of injection temperatures;

4) with 3) product that obtains places the ventilated environment efflorescence to maximum particle size 300～500 orders;

5) with 4) alloy after the efflorescence that obtains places the aqueous sodium hydroxide solution of 10～25 heavy %, stirs 0.5～5 hour in 0～50 ℃, to neutral, promptly gets described catalyzer with the deionized water wash solid product.