CN1475472A - Preparation method of 1,3-poly propylene glycol - Google Patents
Preparation method of 1,3-poly propylene glycol Download PDFInfo
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- CN1475472A CN1475472A CNA031295924A CN03129592A CN1475472A CN 1475472 A CN1475472 A CN 1475472A CN A031295924 A CNA031295924 A CN A031295924A CN 03129592 A CN03129592 A CN 03129592A CN 1475472 A CN1475472 A CN 1475472A
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Abstract
A process for preparing 1,3-propanediol features that the 3-hydroxy propanal is hydrogenated under existance of carried noble metal catalyst whose active components are chosen from Pd, Pt, Au and Rh. Its advantages are cyclic use of catalyst, and high output rate (more than 99.8%).
Description
Technical field
The present invention relates to a kind of 1, the preparation method of ammediol, being specifically related to the 3-hydroxy propanal is feedstock production 1, the method for ammediol is raw material hydrogenation reaction preparation 1 with the 3-hydroxy propanal particularly, the catalyzer of ammediol.
Background technology
1, ammediol is a kind of broad-spectrum compound, and except that can be used for solvent, antifreezing agent, protective material, polyester and polyurethane industrial will be counted in its most important applications field.Studies show that in recent years, with 1, ammediol is a monomer synthetic trevira (PTT) than being that monomer synthetic trevira (PET) has more excellent characteristic with ethylene glycol, it makes ptt fiber both have the performance of PET, the good rebound resilience and the antifouling property that have nylon again, at carpet, engineering plastics, fully developing talents in fields such as garment material, is synthon hot of research and development in the world at present.Poly terephthalic acid 1, the ammediol ester fiber was just succeeded in developing as far back as nineteen forty-one, but because 1, and the costing an arm and a leg of ammediol makes poly terephthalic acid 1, and the development of ammediol ester fiber stays cool for many years always.
The nineties in 20th century, ammediol synthetic novel process made a breakthrough along with 1, and cost constantly descends, and just makes poly terephthalic acid 1, and the exploitation of ammediol ester fiber receives publicity heavily again.
Be used for 3-3-hydroxyl propionaldehyde hydrogenation to produce 1, the catalyzer of ammediol is divided into: 1.Raney type catalyzer, and add the metal that some have promoting catalysis; 2. be the catalyzer of carrier with metal oxide or gac, active ingredient is platinum or palladium; 3. be the catalyzer of carrier with the molecular sieve, active ingredient is a nickel.
It is catalyzer that WO98/57913 selects the metal oxide of load ruthenium or gac for use, carries out the hydrogenation reaction of 3-hydroxy propanal, and the characteristics of this catalyzer are to have advantages of high catalytic activity under lower pressure.When the gac with load 5% ruthenium is a catalyzer, at 40 ℃, 4.0Mpa, 1.0h
-1When carrying out hydrogenation reaction under the air speed, the transformation efficiency of 3-hydroxy propanal can reach 99.7%, but the hydrogenation activity reduction is very fast, and after 96 hours, transformation efficiency reduces to 60%.
It is catalyzer that US5171998 selects Raney's nickel for use, at 13.5Mpa, carry out the hydrogenation reaction of 3-hydroxy propanal under 75 ℃, the transformation efficiency of 3-hydroxy propanal is more than 99%, and 1, the selectivity of ammediol is also more than 99.5%, but because the physical strength of Raney's nickel is low, only be suitable for still reaction, need catalyzer and reactants separate after the reaction, and the catalyzer that reclaims can not reuse, and therefore limited the application of Raney's nickel in industrial-scale production.
US5334778 has narrated a kind of 3-of being used for 3-hydroxyl propionaldehyde hydrogenation to produce and has been equipped with 1, the Ni/Al of ammediol
2O
3/ SiO
2Type catalyzer (content of Ni is about 30%) is 55 ℃ at hydrogenation temperature, hydrogen pressure 10Mpa, and air speed is 0.8h
-1Condition under, carry out the hydrogenation reaction of 3-hydroxy propanal, the transformation efficiency of 3-hydroxy propanal is 96.5%, 1, the selectivity of ammediol is 98%.Its shortcoming is that hydrogenation activity reduces comparatively fast, hydrogenation pressure is higher, reaction velocity is low, and active nickel class catalyzer can form the soluble nickel compounds in the process of hydrogenation, dissolve among the product, making quite difficulty of the separation of catalyzer from reaction solution needs to add diatomite and just can separate usually in reaction solution, make catalyzer to reuse like this.
Summary of the invention
It is a kind of 1 that the technical issues that need to address of the present invention provide, the preparation method of ammediol, and to overcome active low that hydrogenation catalyst that prior art exists exists, defective such as hydrogenation pressure is higher.
Method of the present invention comprises the steps:
The 3-hydroxy propanal is being carried out the two-part hydrogenation reaction with hydrogen in the presence of the loaded noble metal catalyst under normal pressure or low pressure and room temperature or low temperature, first section reaction pressure with second section is identical, but temperature of reaction difference, first section temperature of reaction is 30～100 ℃, because the concentration of reaction later stage 3-hydroxy propanal is thinning, low temperature hydrogenation speed is slow, and second section hydrogenation temperature is increased to 110～120 ℃, and the 3-hydroxy propanal is transformed fully.
Addressed-hydroxy propanal can adopt US5015789 patent or refining of petroleum and chemical industry 2001,32 (12): disclosed method is prepared in 21～24.
The loaded noble metal catalyst of being addressed is by the stable carrier of described system is constituted with the rare metal that is carried on this carrier;
The rare metal of being addressed comprises one or more in palladium, platinum, gold or the rhodium, preferred palladium or platinum, and its amount is the 0.1-10wt% of total catalyst weight;
The carrier of being addressed is a carrier well known in the art, comprises gac, silicon-dioxide, aluminum oxide or molecular sieve, is preferably aluminum oxide.
The aluminum oxide of being addressed has special duct and surface tissue, and its mean pore size is 65.7 , and specific surface area is 233m
2/ g, the acid amount that the surface records is 0.5mmol/g.When the carbonyl hydrogen of 3-hydroxy propanal, carbonyl is after absorption on the acidic site, and fully activation is reacted with the active H that is adsorbed on the Pt position, and the hydrogenation reaction that makes the 3-hydroxy propanal is carried out under normal pressure or low pressure and room temperature or the low temperature under condition as mild as a dove.
Preferred hydrogenation catalyst be on aluminum oxide load the catalyzer of 1～5wt%Pt.
Said catalyzer can adopt dipping method well known in the art to be prepared.
Catalyst consumption must be enough to make raw material change into 1 in the presence of hydrogenation reagent ammediol.Generally speaking, catalyzer is by the mole of Pt, every mole of 3-hydroxy propanal with about 0.000001 to about 0.001 mole Pt.In entire reaction course, consider that from the 3-hydroxy propanal transformation efficiency of reaction and the economy of technological process the consumption of every mole of 3-hydroxy propanal Pt is the best with 0.0008 mole to about 0.008 mole, preferably 0.00001 to 0.0005 mole.
Reaction pressure is 0.1-1.5Mpa, preferred 0.2-1.0Mpa, especially 0.3-0.7Mpa, and first section temperature of reaction is 20-150 ℃, is preferably 30-100 ℃, especially 30-70 ℃.First section temperature of reaction is to influence 1, one of most important factor of ammediol selectivity, and temperature is too low, and speed of reaction is low, long reaction time; Temperature is too high, and the 3-hydroxy propanal under the catalysis of acid carrier condensation takes place, and has a strong impact on 1, the selectivity of ammediol, and also the by product that generates is difficult to separate, and influences the quality of product; Second section temperature of reaction is 110～120 ℃, and improving temperature is to transform fully in order to react a spot of 3-hydroxy propanal of later stage, improves the purity of product.
The determining of reaction times is to be determined by first section hydrogenation reaction degree.First section hydrogenation time is generally 1～4h, is preferably 2～3h, and the best is 3h.Time is too short, and reaction is not enough, and the concentration of 3-hydroxy propanal of leaving second section high temperature hydrogenation for is too high, at high temperature causes a series of side reaction.
Adopt method of the present invention, not only can once connect and once carry out repeatedly hydrogenation and catalyst activity does not reduce, and obtain in economic especially mode high-quality 1, ammediol.Hydrogenation system 1, the mole yield of ammediol can reach more than 99.8%.Therefore acrolein hydration hydrogenation method proposed by the invention is a kind of highly effective 1, and the preparation method of ammediol has bigger suitability for industrialized production prospect.
Will the invention will be further described by embodiment below the embodiment, in an embodiment:
Embodiment 1 Preparation of catalysts:
Take by weighing a certain amount of false boehmite powder, handle with the acetic acid aqueous solution of 0.1N, the pH value of control slurries is 3～4, adds the tensio-active agent of amount of powder 2wt% simultaneously, filters; Displace water in the filter cake with ethanol, behind 100 ℃ of dry 24h, place retort furnace, temperature programming is carried out roasting with the speed of 50 ℃/30min, and being incubated 4 hours at a certain temperature, it is interior standby that the grinding of cooling back is screened into the Powdered moisture eliminator that places of 300～400 purposes.Taking by weighing the above-mentioned alumina powder of handling well of 10g, to place concentration be the 0.8wt% chloroplatinic acid aqueous solution, and dipping 1.5h then, adds the formaldehyde solution reduction of 40ml40wt% again, washing and filtering, and vacuum-drying obtains the Pt/Al that Pt content is 3wt%
2O
3Catalyzer.
Embodiment 2
The aqueous solution of the 3-hydroxy propanal of about 6% (weight) of adding 40ml and 0.1gPt content are 3% Pt/Al in the stainless steel compressive reaction still of 250ml
2O
3Catalyzer.Sealing back is earlier with nitrogen replacement 3 times, heats up with behind the hydrogen exchange 3 times again, starts stirring when temperature rises to 50 ℃, hydrogen pressure maintained 1.0Mpa, constant temperature 3h; Temperature is increased to 120 ℃ again and continues reaction, till no longer inhaling hydrogen, be cooled to emptying after the room temperature, suction filtration is isolated catalyzer, and sampling is analyzed.The transformation efficiency that records the 3-hydroxy propanal is 93.6%, generates 1, and the selectivity of ammediol is 100%.
Embodiment 3
The aqueous solution of the 3-hydroxy propanal of about 6% (weight) of adding 40ml and 0.3gPd content are 5% Pd/ activated-carbon catalyst in the stainless steel compressive reaction still of 250ml.Sealing back is earlier with nitrogen replacement 3 times, heats up with behind the hydrogen exchange 3 times again, starts stirring when temperature rises to 50 ℃, hydrogen pressure maintained 1.0Mpa, constant temperature 3h; Temperature is increased to 120 ℃ again and continues reaction, till no longer inhaling hydrogen, be cooled to emptying after the room temperature, suction filtration is isolated catalyzer, and sampling is analyzed.The transformation efficiency that records the 3-hydroxy propanal is 87.6%, generates 1, and the selectivity of ammediol is 100%.
Embodiment 4
The aqueous solution of the 3-hydroxy propanal of about 6% (weight) of adding 40ml and 0.3gPt-Rh (1: 1) content are 3% Pt-Rh/Al in the stainless steel compressive reaction still of 250ml
2O
3Catalyzer.Sealing back is earlier with nitrogen replacement 3 times, heats up with behind the hydrogen exchange 3 times again, starts stirring when temperature rises to 50 ℃, hydrogen pressure maintained 1.0Mpa, constant temperature 2h; Temperature is increased to 110 ℃ again and continues reaction, till no longer inhaling hydrogen, be cooled to emptying after the room temperature, suction filtration is isolated catalyzer, and sampling is analyzed.The transformation efficiency that records the 3-hydroxy propanal is 94.5%, generates 1, and the selectivity of ammediol is 95.3%.
Embodiment 5
The aqueous solution of the 3-hydroxy propanal of about 6% (weight) of adding 40mml and 0.3gPt content are 3% Pt/ activated-carbon catalyst in the stainless steel compressive reaction still of 250ml.Sealing back is earlier with nitrogen replacement 3 times, heats up with behind the hydrogen exchange 3 times again, starts stirring when temperature rises to 50 ℃, hydrogen pressure maintained 1.0Mpa, constant temperature 3h; Temperature is increased to 110 ℃ again and continues reaction, till no longer inhaling hydrogen, be cooled to emptying after the room temperature, suction filtration is isolated catalyzer, and sampling is analyzed.The transformation efficiency that records the 3-hydroxy propanal is 75.8%, generates 1, and the selectivity of ammediol is 98.0%.
Embodiment 6
The aqueous solution of the 3-hydroxy propanal of about 6% (weight) of adding 40ml and 0.3g Pt/ content are 0.5% Pt/Al in the stainless steel compressive reaction still of 250ml
2O
3Catalyzer.Sealing back is earlier with nitrogen replacement 3 times, heats up with behind the hydrogen exchange 3 times again, starts stirring when temperature rises to 60 ℃, hydrogen pressure maintained 1.0Mpa, constant temperature 3h; Temperature is increased to 115 ℃ again and continues reaction, till no longer inhaling hydrogen, be cooled to emptying after the room temperature, suction filtration is isolated catalyzer, and sampling is analyzed.The transformation efficiency that records the 3-hydroxy propanal is 92.6%, generates 1, and the selectivity of ammediol is 87.0%.
Embodiment 7
The aqueous solution of the 3-hydroxy propanal of about 6% (weight) of adding 40ml and 0.1gPt content are 5% Pt/Al in the stainless steel compressive reaction still of 250ml
2O
3Catalyzer.Sealing back is earlier with nitrogen replacement 3 times, heats up with behind the hydrogen exchange 3 times again, starts stirring when temperature rises to 100 ℃, hydrogen pressure maintained 1.0Mpa, constant temperature 2h; Temperature is increased to 110 ℃ again and continues reaction, till no longer inhaling hydrogen, be cooled to emptying after the room temperature, suction filtration is isolated catalyzer, and sampling is analyzed.The transformation efficiency that records the 3-hydroxy propanal is 90.0%, generates 1, and the selectivity of ammediol is 43.2%.
Embodiment 8
The aqueous solution of the 3-hydroxy propanal of about 6% (weight) of adding 40ml and 0.3gPt content are 3% Pt/Al in the stainless steel compressive reaction still of 250ml
2O
3Catalyzer.Sealing back is earlier with nitrogen replacement 3 times, heats up with behind the hydrogen exchange 3 times again, starts stirring when temperature rises to 50 ℃, hydrogen pressure maintained 0.6Mpa, constant temperature 3h; Temperature is increased to 120 ℃ again and continues reaction, till no longer inhaling hydrogen, be cooled to emptying after the room temperature, suction filtration is isolated catalyzer, and sampling is analyzed.The transformation efficiency that records the 3-hydroxy propanal is 100%, generates 1, and the selectivity of ammediol is 100%.
Embodiment 9
The aqueous solution of the 3-hydroxy propanal of about 6% (weight) of adding 40ml and 0.3gPt content are 3% Pt/Al in the stainless steel compressive reaction still of 250ml
2O
3Catalyzer.Sealing back is earlier with nitrogen replacement 3 times, heats up with behind the hydrogen exchange 3 times again, starts stirring when temperature rises to 50 ℃, hydrogen pressure maintained 0.3Mpa, constant temperature 4.5h; Temperature is increased to 110 ℃ again and continues reaction, till no longer inhaling hydrogen, be cooled to emptying after the room temperature, suction filtration is isolated catalyzer, and sampling is analyzed.The transformation efficiency that records the 3-hydroxy propanal is 100%, generates 1, and the selectivity of ammediol is 100%.
Claims (9)
1. one kind 1, the preparation method of ammediol is characterized in that, comprises the steps:
The 3-hydroxy propanal is carried out the two-part hydrogenation reaction in the presence of loaded noble metal catalyst, the loaded noble metal catalyst of being addressed is by stable carrier of described system and one or more the rare metal that is carried in palladium, platinum, gold or the rhodium on this carrier are constituted.
2. method according to claim 1 is characterized in that, the rare metal amount is the 0.1-10wt% of total catalyst weight.
3. method according to claim 2 is characterized in that, the catalyzer of being addressed on aluminum oxide load the catalyzer of 1～5wt%Pt.
4. method according to claim 1 is characterized in that the carrier of being addressed comprises gac, silicon-dioxide, aluminum oxide or molecular sieve.
5. method according to claim 4 is characterized in that, carrier is an aluminum oxide.
6. according to each described method of claim 1～5, it is characterized in that reaction pressure is 0.1-1.5Mpa, first section temperature of reaction is 30-100 ℃, and second section temperature is 110-120 ℃.
7. according to each described method of claim 1～5, it is characterized in that, the 3-hydroxy propanal is being carried out the two-part hydrogenation reaction with hydrogen in the presence of the loaded noble metal catalyst under normal pressure or low pressure and room temperature or low temperature, first section temperature of reaction is 30～100 ℃, and second section temperature of reaction is 110～120 ℃.
8. according to each described method of claim 1～5, it is characterized in that, catalyst consumption, by the mole of Pt, every mole of 3-hydroxy propanal with about 0.000001 to about 0.001 mole Pt.
9. method according to claim 8 is characterized in that, catalyst consumption, by the mole of Pt, every mole of 3-hydroxy propanal with about 0.000001 to about 0.001 mole Pt.
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| CNA031295924A CN1475472A (en) | 2003-06-30 | 2003-06-30 | Preparation method of 1,3-poly propylene glycol |
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| CNA031295924A CN1475472A (en) | 2003-06-30 | 2003-06-30 | Preparation method of 1,3-poly propylene glycol |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102029199A (en) * | 2010-11-15 | 2011-04-27 | 大连理工大学 | Method for preparing load-type noble metal nanometer catalyst by solvent-free microwave-assisted pyrolysis method |
| JP2014513053A (en) * | 2011-02-16 | 2014-05-29 | ヘイロウカーボン プロダクツ コーポレイション | Method for producing fluorinated diol |
| CN114349619A (en) * | 2022-01-13 | 2022-04-15 | 江苏扬农化工集团有限公司 | Method for preparing hydroxy aldehyde through olefine aldehyde hydration reaction |
| WO2022099488A1 (en) * | 2020-11-11 | 2022-05-19 | 中国科学院宁波材料技术与工程研究所 | Precious metal-loaded eggshell type catalyst, preparation method therefor, and application thereof |
| CN115141083A (en) * | 2022-06-19 | 2022-10-04 | 中海油天津化工研究设计院有限公司 | Method for preparing 1, 3-propylene glycol by hydrogenating 3-hydroxypropionaldehyde |
-
2003
- 2003-06-30 CN CNA031295924A patent/CN1475472A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102029199A (en) * | 2010-11-15 | 2011-04-27 | 大连理工大学 | Method for preparing load-type noble metal nanometer catalyst by solvent-free microwave-assisted pyrolysis method |
| JP2014513053A (en) * | 2011-02-16 | 2014-05-29 | ヘイロウカーボン プロダクツ コーポレイション | Method for producing fluorinated diol |
| WO2022099488A1 (en) * | 2020-11-11 | 2022-05-19 | 中国科学院宁波材料技术与工程研究所 | Precious metal-loaded eggshell type catalyst, preparation method therefor, and application thereof |
| CN114349619A (en) * | 2022-01-13 | 2022-04-15 | 江苏扬农化工集团有限公司 | Method for preparing hydroxy aldehyde through olefine aldehyde hydration reaction |
| CN114349619B (en) * | 2022-01-13 | 2024-01-30 | 江苏扬农化工集团有限公司 | Method for preparing hydroxyaldehyde by olefine aldehyde hydration reaction |
| CN115141083A (en) * | 2022-06-19 | 2022-10-04 | 中海油天津化工研究设计院有限公司 | Method for preparing 1, 3-propylene glycol by hydrogenating 3-hydroxypropionaldehyde |
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