CN109970511A - A kind of method of HPPO by-product resource utilization synthesis 1,3- propylene glycol - Google Patents
A kind of method of HPPO by-product resource utilization synthesis 1,3- propylene glycol Download PDFInfo
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- CN109970511A CN109970511A CN201910316117.3A CN201910316117A CN109970511A CN 109970511 A CN109970511 A CN 109970511A CN 201910316117 A CN201910316117 A CN 201910316117A CN 109970511 A CN109970511 A CN 109970511A
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Abstract
The invention belongs to field of chemical technology, it is related to a kind of HPPO by-product resource utilization synthesis 1, the method of 3-propanediol, more specifically, it is related to one kind with HPPO technique oxypropylene and the different methyl ether of methanol reaction product propylene glycol (2- methoxy-1-propanol) for raw material, the 1 of high added value is synthesized through cracking, hydroboration-oxidation two-step reaction, the method of 3-propanediol, 1,85% or more 3-propanediol total recovery, 99.5% or more purity, the present invention has the characteristics that simple process route, Resource Rationalization utilization, 1,3-PD yield and purity is high.
Description
Technical field
The invention belongs to field of chemical technology, it is related to a kind of HPPO by-product resource utilization synthesis 1,3-PD
Method, more particularly, to one kind with HPPO technique oxypropylene and methanol reaction product propylene glycol different methyl ether (2- methoxy
Base -1- propyl alcohol) it is raw material, the method through cracking, the 1,3-PD of hydroboration-oxidation two-step reaction synthesis high added value, 1,3-
85% or more propylene glycol total recovery, 99.5% or more purity, the present invention have process route is simple, Resource Rationalization utilizes, 1,
The features such as 3-propanediol yield and purity is high.
Background technique
1,3-PD (1,3-Propanediol) is a kind of important industrial chemicals, be mainly used as polymer monomer with
P-phthalic acid (PTA) synthesizing new polyester material --- polypropylene terephthalate (PTT), PTT both have poly- pair
The chemical stability of ethylene terephthalate (PET), while there is good resilience performance and resistance tocrocking, in engineering plastic
The fields such as material, textile possess good application prospect.
Currently, industrially the method for production 1,3-PD specifically includes that acrolein hydration method, epoxyethane method, glycerol
Catalytic hydrogenolysis method and microbe fermentation method.Acrolein hydration method and epoxyethane method technique are cumbersome, complicated for operation, by-product is more,
High temperature and pressure and intermediate strong toxicity are generally required, there are serious security risks, fill at present using the production of both methods
It sets and generally stops production.Glycerin catalytic hydrogenolysis method be by glycerol hydrogenolysis catalyst effect under, be converted into 1,3-PD, 1,2- third
The products such as glycol, ethylene glycol, the method 1,3-PD poor selectivity and yield is low.Although microbe fermentation method has reaction condition
Mildly, easy to operate, advantages of environment protection, but microbe fermentation method production concentration is low, and separating energy consumption is high, while microorganism sends out
The problems such as bacterial strain that ferment method uses is short there are the service life, active reduction speed is fast.
Patent CN201310457657.6 discloses a kind of method that glycerine hydrogenation prepares 1,3-PD, and this method is being urged
Agent Pt/B2O3-WO3-ZrO2Under effect, glycerol and hydrogen are passed through fixed bed reactors, 100~150 DEG C, anti-under 2.5MPa
1,3-PD should be prepared, but this method can generate more isopropanol, normal propyl alcohol, 1,2-PD, hydrogenation products are complicated, and 1,
3-propanediol yield and selectivity are low.
Patent CN200810186614.8 is disclosed one kind and is reacted with copper-based catalysts catalyzing glycerol steam and hydrogen
The method for generating 1,3-PD, this method use cheap copper-based catalysts, need to vaporize glycerol, and energy consumption is high, and 1,3- the third two
Alcohol selectivity is low with yield.
Patent CN200910089427.2 discloses a kind of method that microbial method prepares 1,3-PD, and this method uses
Cray inha enzyme converts glycerol into 1,3-PD, fermentation time 24 hours or more, obtain containing the dilute of 1,3-PD
Solution concentration only 5% or so, needs to obtain thick 1,3-PD by the methods of flocculation, filtering, concentration, then rectifying is obtained into
Product 1,3-PD, 1,3-PD separating technology is complicated, and energy consumption is high.
Document (Wu Congyi, Chen Jing .1,3- propylene glycol Progress In Preparation [J] Journal of Molecular Catalysis, 2012,26 (3): 276-
283.) it reviews epoxyethane method and acrolein hydration method prepares the mechanism and catalyst system of 1,3-PD, it is indicated that mesh
Preceding both methods catalyst choice and stability, process complexity and in terms of defect limit it and answer
With.
HPPO method prepares propylene oxide, Titanium Sieve Molecular Sieve, hydrogen peroxide, methanol, propylene system usually in a mild condition
Middle generation epoxidation reaction generates propylene oxide.In methanol system, propylene oxide is under acid centre catalytic action, meeting and first
Alcohol reaction generates the different methyl ether of propylene glycol.Existing lipophilic covalent ehter bond in the different methyl ether molecular structure of propylene glycol can dissolve oleophylic
Property substance, and have hydrophilic alcoholic extract hydroxyl group, can dissolve water-soluble substances, therefore the different methyl ether of propylene glycol is a kind of excellent versatility
Solvent.
It is industrial at present that the different methyl ether of propylene glycol is mainly used as coating, ink, printing and dyeing, pesticide, cellulose, acrylate etc.
Solvent, dispersing agent and diluent, also serve as antifreezing agent, cleaning agent, extractant, non-ferrous metal ore agent etc..Above-mentioned industry pair
The different methyl ether demand of propylene glycol is relatively stable, and the different methyl ether downstream demand of propylene glycol increasess slowly.But with domestic HPPO device
Quickly start, the different methyl ether of the propylene glycol of by-product faces the serious superfluous problem of production capacity, and at the same time, domestic PTT demand quickly increases
Long, existing 1,3-PD production capacity increases limited, it is difficult to meet the needs of PTT rapid growth.Therefore, it develops a kind of by HPPO pair
The different methyl ether of the propylene glycol of production, which is converted into 1,3- propylene glycol process route, has greatly society and economic value.It is existing through consulting
Technology is not using the different methyl ether of propylene glycol as the report of Material synthesis 1,3- propylene glycol.
The present invention synthesizes the 1 of high added value using the different methyl ether of propylene glycol as raw material, through cracking, hydroboration-oxidation two-step reaction,
3-propanediol, has not only widened the downstream application of the different methyl ether of propylene glycol of by-product in HPPO technique, but also develops a kind of efficient
The method for synthesizing 1,3-PD, simple, Resource Rationalization utilization, good economy performance, 1,3-PD yield with process route
And the features such as purity is high.
Summary of the invention
The object of the present invention is to provide a kind of synthesis sides of polypropylene terephthalate (PTT) monomer 1,3- propylene glycol
Method is closed more particularly, to the different methyl ether of propylene glycol using HPPO method by-product as raw material through cracking, hydroboration-oxidation two-step reaction
At the process route of the 1,3-PD of high added value, 85% or more 1,3-PD yield, 99.5% or more product purity.This
Invention has many advantages, such as simple process route, Resource Rationalization utilization, 1,3- propylene glycol yield and purity is high.Synthesize 1,3- the third two
The chemical equation of alcohol is as follows:
The purpose of the present invention is what is be realized by the following method:
A method of using the different methyl ether of HPPO by-product propylene glycol as Material synthesis 1,3-PD, include the following steps:
(1) cracking reaction: the different methyl ether of propylene glycol is pumped into the shell and tube reactor equipped with catalyst, in certain temperature and
With certain air speed by catalyst bed under pressure, obtained product separates methanol therein, obtains propenyl crude product；
(2) under the conditions of nitrogen protection, hydroboration hydroboration-oxidation: is added to propenyl obtained in step (1)
Hydroboration occurs at a certain temperature for reagent, after reaction, is slow added into a certain amount of aqueous slkali and peroxidating examination
Agent, is stirred to react a period of time, and reaction solution obtains 1,3-PD through liquid separation, extraction, distillation；
Catalyst described in above-mentioned steps (1) is made of carrier and active material, and carrier is selected from aluminium oxide, titanium dioxide
One of silicon, ion exchange resin, silica gel, active carbon and Si-Al molecular sieve or a variety of mixing；Active material is selected from sulfuric acid
One of aluminium, aluminium chloride, copper sulphate, ferric sulfate, nickel sulfate, titanium oxide, zirconium oxide, heteropoly acid, precious metal cation are more
The mixing of kind, active material load capacity are the 0.1%~10% of carrier quality；
Reaction temperature described in above-mentioned steps (1) is 120-300 DEG C, reaction pressure 0.3-2MPa；
The mass space velocity of the different methyl ether of propylene glycol described in above-mentioned steps (1) is 1~10h-1；
Hydroborating agents described in above-mentioned steps (2) are monoborane, diborane, bicyclic [3.3.1] nonane (9- of 9- boron
) etc. BBN the tetrahydrofuran or one of ether or dimethyl sulphide solution of common hydroborating agents and a variety of mixing, dosage are
0.8~3 times of propenyl molal quantity；
Hydroboration temperature described in above-mentioned steps (2) be 0~80 DEG C, the reaction time be 1~for 24 hours；
Lye described in above-mentioned steps (2) is one of sodium carbonate, sodium bicarbonate or sodium hydroxide solution, alkali concentration
For 0.1~5mol/L, dosage is 1~5 times of propenyl quality；
Peroxidic reagents described in above-mentioned steps (2) be hydrogen peroxide, dialkyl peroxide, diacyl peroxide,
One or more mixing of the common peroxide such as peroxy acid, peroxy esters, dosage are 0.8~1.5 times of propenyl molal quantity；
The present invention provides a kind of synthetic routes of 1,3-PD, have the advantage that
(1) Resource Rationalization utilizes, is good in economic efficiency: reacting the different methyl ether of propylene glycol generated with methanol using propylene oxide
For raw material, the higher PTT monomer 1,3-PD of added value is synthesized, the downstream application of the different methyl ether of propylene glycol has been widened, had good
Good economic benefit.
(2) process route is simple: the different methyl ether of propylene glycol synthesizes 1,3- the third two through cracking, hydroboration-oxidation two-step reaction
Alcohol, process route is simple, and using the Green Oxidants such as hydrogen peroxide, technique cleaning, three wastes discharge amount is few.
(3) 1,3-PD yield and purity is high: 85% or more 1,3-PD total recovery, 99.5% or more purity.
Specific embodiment
The following examples illustrate the present invention in more detail, rather than limitation of the invention further.Unless
It is otherwise noted, " % " therein is " quality % ".
Embodiment 1
By the different methyl ether of 720g propylene glycol with mass space velocity 5h-1It is pumped into equipped with CuSO4/SiO2Catalyst (CuSO4Load capacity
1%) in shell and tube reactor, control reaction temperature is 150 DEG C, reaction pressure 0.6MPa, reacts on-line analysis propylene glycol
Different methyl ether conversion ratio 99.2%, propenyl selectivity 99.0%, obtained product obtains 445.7g propenyl after separating methanol
Crude product (normalizing content 99.1%) yield is 95.2%.
Embodiment 2-6
On the basis of embodiment 1, change the type and active material load capacity and the temperature of reaction, pressure of catalyst
And air speed, other conditions are constant, synthesize propenyl, and acquired results are as shown in the table.
Embodiment 7
Under the conditions of nitrogen protection, the monoborane four of 7000g is added in gained 445.7g propenyl crude product into embodiment 1
Hydrogen tetrahydrofuran solution (monoborane concentration 1.2mol/L), after 3 hours are stirred to react at 30 DEG C, is slowly added into reaction solution
1000g 1mol/L sodium bicarbonate solution, adds the hydrogen peroxide of 820g 35%, is stirred at room temperature 4 hours, after reaction, instead
Liquid liquid separation is answered to obtain oil reservoir and water layer, water layer 800g tetrahydrofuran extracts three times, and extraction oil reservoir merges warp with oil reservoir obtained by liquid separation
Dehydration, distillation obtain 535.3g 1,3-PD (purity 99.5%), 1,3-PD to propenyl yield 91.6%,
To the different methyl ether yield 87.6% of the propylene glycol of investment.
Embodiment 8-11
On the basis of embodiment 7, change the hydroborating agents of addition and the type of peroxidic reagents and dosage and anti-
The time answered and temperature, other conditions are constant, synthesize 1,3-PD, and acquired results are as shown in the table.
Content of the present invention is not limited in embodiment content of the present invention.
Specific case used herein is expounded structure of the invention and embodiment, the explanation of above embodiments
It is merely used to help understand the core idea of the present invention.It should be pointed out that for those skilled in the art,
Without departing from the principles of the invention, can be with several improvements and modifications are made to the present invention, these improvement and modification are also fallen
Enter in the protection scope of the claims in the present invention.
Claims (8)
1. a kind of using the different methyl ether of HPPO by-product propylene glycol as the method for Material synthesis 1,3-PD, which is characterized in that including such as
Lower step:
(1) cracking reaction: the different methyl ether of propylene glycol is pumped into the shell and tube reactor equipped with catalyst, in certain temperature and pressure
Under with certain air speed by catalyst bed, obtained product separates methanol therein, obtains propenyl crude product；
(2) hydroboration-oxidation: under the conditions of nitrogen protection, being added hydroborating agents to propenyl obtained in step (1),
Hydroboration occurs at a certain temperature, after reaction, is slow added into a certain amount of aqueous slkali and peroxidic reagents, stirs
Reaction a period of time is mixed, reaction solution obtains 1,3-PD through liquid separation, extraction, distillation.
2. it is according to claim 1 using the different methyl ether of HPPO by-product propylene glycol as the method for Material synthesis 1,3-PD,
It is characterized in that, catalyst described in above-mentioned steps (1) is made of carrier and active material, and carrier is selected from aluminium oxide, titanium dioxide
One of silicon, active carbon and Si-Al molecular sieve or a variety of mixing；Active material is selected from aluminum sulfate, aluminium chloride, copper sulphate, sulphur
One of sour iron, nickel sulfate, titanium oxide, zirconium oxide, heteropoly acid or a variety of mixing, active material load capacity are carrier quality
0.1%~10%.
3. it is according to claim 1 using the different methyl ether of HPPO by-product propylene glycol as the method for Material synthesis 1,3-PD,
It is characterized in that, reaction temperature described in above-mentioned steps (1) is 120-300 DEG C, reaction pressure 0.3-2MPa.
4. it is according to claim 1 using the different methyl ether of HPPO by-product propylene glycol as the method for Material synthesis 1,3-PD,
It is characterized in that, the mass space velocity of the different methyl ether of propylene glycol described in above-mentioned steps (1) is 1~10h-1。
5. it is according to claim 1 using the different methyl ether of HPPO by-product propylene glycol as the method for Material synthesis 1,3-PD,
It is characterized in that, hydroborating agents described in above-mentioned steps (2) are monoborane, diborane, bicyclic [3.3.1] nonane (9- of 9- boron
BBN one of tetrahydrofuran, ether or dimethyl sulphide solution) and a variety of mixing, dosage are the 0.8 of propenyl molal quantity
~3 times.
6. it is according to claim 1 using the different methyl ether of HPPO by-product propylene glycol as the method for Material synthesis 1,3-PD,
Be characterized in that, hydroboration temperature described in above-mentioned steps (2) be 0~80 DEG C, the reaction time be 1~for 24 hours.
7. it is according to claim 1 using the different methyl ether of HPPO by-product propylene glycol as the method for Material synthesis 1,3-PD,
It is characterized in that, lye described in above-mentioned steps (2) is one of sodium carbonate, sodium bicarbonate or sodium hydroxide solution, alkali dense
Degree is 0.1~5mol/L, and dosage is 1~5 times of propenyl quality.
8. it is according to claim 1 using the different methyl ether of HPPO by-product propylene glycol as the method for Material synthesis 1,3-PD,
Be characterized in that, peroxidic reagents described in above-mentioned steps (2) be hydrogen peroxide, dialkyl peroxide, diacyl peroxide,
One or more mixing of peroxy acid, peroxy esters, dosage are 0.8~1.5 times of propenyl molal quantity.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110746269A (en) * | 2019-11-06 | 2020-02-04 | 山西中医药大学 | Synthesis method of 1, 3-propylene glycol |
| CN111018664A (en) * | 2019-12-27 | 2020-04-17 | 江苏广域化学有限公司 | Synthesis method of 2-alkyl-1, 3-propanediol compound |
| CN112592257A (en) * | 2020-12-21 | 2021-04-02 | 大连理工大学 | Preparation method of coal-based 1, 3-propylene glycol |
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| WO2012092512A2 (en) * | 2010-12-31 | 2012-07-05 | California Institute Of Technology | Catalytic anti-markovnikov oxidation and hydration of olefins |
| CN107721821A (en) * | 2017-10-13 | 2018-02-23 | 北京博迩科技有限公司 | A kind of method for preparing 1,3 propane diols |
| CN108586193A (en) * | 2018-05-30 | 2018-09-28 | 深圳市前海博扬研究院有限公司 | A method of preparing 1,3-PD using 3- methoxy methyl propionates |
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| CN110746269A (en) * | 2019-11-06 | 2020-02-04 | 山西中医药大学 | Synthesis method of 1, 3-propylene glycol |
| CN111018664A (en) * | 2019-12-27 | 2020-04-17 | 江苏广域化学有限公司 | Synthesis method of 2-alkyl-1, 3-propanediol compound |
| CN111018664B (en) * | 2019-12-27 | 2023-04-14 | 江苏广域化学有限公司 | Synthesis method of 2-alkyl-1, 3-propanediol compound |
| CN112592257A (en) * | 2020-12-21 | 2021-04-02 | 大连理工大学 | Preparation method of coal-based 1, 3-propylene glycol |
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