CN103820226A - Method for preparing swill-cooked dirty oil modified polyester polyol from recovered alcohol and swill-cooked dirty oil - Google Patents
Method for preparing swill-cooked dirty oil modified polyester polyol from recovered alcohol and swill-cooked dirty oil Download PDFInfo
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- CN103820226A CN103820226A CN201310655152.0A CN201310655152A CN103820226A CN 103820226 A CN103820226 A CN 103820226A CN 201310655152 A CN201310655152 A CN 201310655152A CN 103820226 A CN103820226 A CN 103820226A
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- sewer oil
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Abstract
The invention discloses a method for preparing swill-cooked dirty oil modified polyester polyol from recovered alcohol and swill-cooked dirty oil. The method comprises the following steps: 1) putting a low-molecular polyol, swill-cooked dirty oil and a catalyst into a polyester reaction kettle; 2) heating to 140 to 150 DEG C and reacting for 1 to 1.5 hours; 3) introducing N2, continuously heating to 180 to 190 DEG C and reacting for 1.5 to 2 hours; 4) continuously heating to 220 to 230 DEG C and preserving heat for 4 to 5 hours; (5) stopping heating, cooling to 120 DEG C, stopping the nitrogen, vacuumizing, reacting for 1.5 to 2 hours and stopping reaction when the water content of the product is less than or equal to 0.07; 6) cooling the obtained product to be below 75 DEG C and discharging. The swill-cooked dirty oil modified polyester polyol product has high reaction activity, can improve the caking property, the hydrolysis resistance and the impact resistance of polyurethane products and can reduce the using amount of the catalyst. The production cost is low, and environmental friendliness and recycling of the waste alcohol and the swill-cooked dirty oil can be realized.
Description
Technical field
The present invention relates to a kind of preparation method of sewer oil modified poly ester polyvalent alcohol, especially a kind of method of utilizing recovery alcohol and sewer oil to prepare sewer oil modified poly ester polyvalent alcohol.
Background technology
Sewer oil derives from the edible oil of decocting after stir-fry, is to fish for from the trench oil trap of catering trade, and through simply heating, dewater, remove slag, the grease that extracts of the technique such as precipitation, its main component remains triglyceride level.Now, because China does not reasonably utilize sewer oil, cause sewer oil to become a kind of environmental pollutant, and the healthy of people arrived in serious threat.Therefore, realizing as early as possible the disposal and utilization of sewer oil or swill oil, reach minimizing environmental pollution, bring into play to greatest extent the object of the use value of sewer oil or swill oil, is that current sewer oil or swill oil are processed problem demanding prompt solution in research.
China mainly contains three kinds of modes to the comprehensive utilization of sewer oil at present: the one, and sewer oil is carried out to simple processing and purify, directly as low-grade industrial oleic acid, stearic acid and commercial grease etc., the 2nd, utilize sewer oil to prepare non-phosphide detergent, the 3rd, by sewer oil alcoholysis preparing biological diesel oil (fatty acid methyl ester).
A kind of method of being prepared grease-based polyol by sewer oil direct esterification transesterify is disclosed in Chinese patent CN103275306A.This method is to be first 10～30: 1 in mass ratio by sewer oil and polyvalent alcohol, is at 150～250 ℃ in temperature, reacts 2～12 hours, and reaction process vacuumizes the water of sloughing in reaction, and vacuum tightness is-0.075MPa～-0.050MPa, obtains pre-esterification products; Then by the pre-esterification products obtaining with polyvalent alcohol, catalyzer under N2 protection, temperature is 100～250 ℃, reacts 1～10 hour, removes by filter catalyzer, obtains grease-based polyol, wherein the mol ratio of esterification products and polyvalent alcohol is 1: 1～6 in advance.
The pre-treating technology of sewer oil is generally as follows: temperature warm alkali refining-washing stratification-be dried-refining sewer oil in that comes unstuck in the thick oily centrifuging removal of impurities one of sewer oil.
Summary of the invention
Being the low molecular polylol reclaiming and carrying out esterification transesterification reaction through the sewer oil of pre-treatment of utilization of the present invention, can accomplish to make the best use of everything, environmental protection and production cost are relatively low, and product has more market competition advantage, and the technical scheme solving the problems of the technologies described above is:
Utilize recovery alcohol and sewer oil to prepare a method for sewer oil modified poly ester polyvalent alcohol, comprise the following steps:
1) by low molecular polylol raw material and sewer oil and catalyzer input pet reaction still;
2) method that adopts high temperature oil bath to heat, is warming up to 140～150 ℃, reaction 1～1.5h;
3) pass into N
2make protection gas, make still internal pressure maintain 0.01MPa, continue to be warming up to 180～190 ℃, reaction 1.5～2h;
4) continue to be warming up to 220～230 ℃, insulation 4～5h;
5) stop heating, be cooled to 120 ℃, close nitrogen, start to vacuumize, vacuum tightness and temperature are finally stabilized in 0.08～0.095Mpa, 120～125 ℃ separately, react 1.5～2h, until product moisture≤0.07 o'clock stopped reaction;
6) be cooled to 75 ℃ with bottom discharge, obtain sewer oil modified poly ester polyvalent alcohol.
Further, described low molecular polylol raw material refers to recovery alcohol mixture, mainly reclaims ethylene glycol, glycerine and Diethylene Glycol.
Further, contained two senses and polyvalent alcohols more than two senses in described low molecular polylol raw material, with the mol ratio of sewer oil be 2.0～3.5.
Further, the mass percent of the recovery glycerine in described recovery alcohol mixture is not more than 35%.
Further, described recovery alcohol mixture and the colourity of sewer oil all in 150Hazen, and are transparent liquid.
Further, the hydroxyl value scope of described recovery alcohol mixture is 1000～1250mg KOH/g.
Further, in described recovery alcohol mixture, content is not less than 90%, and other impurity can be water, small molecules polyvalent alcohol and ester class any one or a few.
Further, described small molecules polyvalent alcohol and the molecular weight of ester class are all in 240g/mol, and boiling point is all less than 300 ℃.
Further, described catalyzer is potassium hydroxide, and accounts for 0.01～0.03% of all raw material total masses.
Adopt such scheme, obtained a kind of sewer oil modified poly ester polyvalent alcohol.It is raw material with reclaiming alcohol that the present invention utilizes through the sewer oil of pre-treatment, prepares the polyester polyol of different hydroxyl values through esterification transesterify.Utilize this polyester polyol to prepare breakwater glue, have good glueability, withstand shock vibrations and very high stripping strength, particularly have good hydrolytic resistance.
Sewer oil modified poly ester polyvalent alcohol product reactive behavior of the present invention is high, can increase cohesiveness, hydrolytic resistance, the shock-resistance of polyurethane product simultaneously, reduces catalyst levels.Take the low molecular polylol that reclaims and sewer oil as raw material, production cost is low, can realize the environmental protection recycling of useless alcohol and sewer oil simultaneously.
Accompanying drawing explanation
Below in conjunction with the drawings and specific embodiments, the present invention is further detailed explanation.
Fig. 1 is operation step map of the present invention.
Embodiment
Embodiment 1:
1) 93Kg being reclaimed to alcohol (hydroxyl value 1000mg KOH/g) drops into respectively in pet reaction still with 27Kg sewer oil and 12g catalyzer;
2) method that adopts high temperature oil bath to heat, is warming up to 145 ℃, reaction 1.5h;
3) pass into N
2make protection gas, make still internal pressure maintain 0.01MPa, continue to be warming up to 180 ℃, reaction 1.5h;
4) continue to be warming up to 225 ℃, insulation 4h;
5) stop heating, be cooled to 120 ℃, close nitrogen, start to vacuumize, vacuum tightness and temperature are finally stabilized in 0.09MPa, 120 ℃ of left and right, stopped reaction after 2h separately;
6) be cooled to 75 ℃ with bottom discharge, obtain the sewer oil modified poly ester polyvalent alcohol (hydroxyl value 400mg KOH/g, moisture 0.03%) of liquid clear.
Embodiment 2:
1) 90Kg being reclaimed to alcohol (hydroxyl value 1150mg KOH/g) drops into respectively in pet reaction still with 40Kg sewer oil and 20g catalyzer;
2) method that adopts high temperature oil bath to heat, is warming up to 145 ℃, reaction 2h;
3) pass into N
2make protection gas, make still internal pressure maintain 0.01MPa, continue to be warming up to 180 ℃, reaction 2h;
4) continue to be warming up to 225 ℃, insulation 5h;
5) stop heating, be cooled to 120 ℃, close nitrogen, start to vacuumize, vacuum tightness and temperature are finally stabilized in 0.09MPa, 120 ℃ of left and right, stopped reaction after 2h separately;
6) be cooled to 75 ℃ with bottom discharge, obtain the sewer oil modified poly ester polyvalent alcohol (hydroxyl value 490mg KOH/g, moisture 0.04%) of liquid clear.
Embodiment 3:
1) 92Kg being reclaimed to alcohol (hydroxyl value 1050mg KOH/g) drops into respectively in pet reaction still with 33Kg sewer oil and 25g catalyzer;
2) method that adopts high temperature oil bath to heat, is warming up to 145 ℃, reaction 1.8h;
3) pass into N
2make protection gas, make still internal pressure maintain 0.01MPa, continue to be warming up to 180 ℃, reaction 1.5h;
4) continue to be warming up to 225 ℃, insulation 5h;
5) stop heating, be cooled to 120 ℃, close nitrogen, start to vacuumize, vacuum tightness and temperature are finally stabilized in 0.09MPa, 120 ℃ of left and right, stopped reaction after 2h separately;
6) be cooled to 75 ℃ with bottom discharge, obtain the sewer oil modified poly ester polyvalent alcohol (hydroxyl value 450mg KOH/g, moisture 0.04%) of liquid clear.
Embodiment 4:
1) 66Kg being reclaimed to alcohol (hydroxyl value 1250mg KOH/g) drops into respectively in pet reaction still with 34Kg sewer oil and 30g catalyzer;
2) method that adopts high temperature oil bath to heat, is warming up to 145 ℃, reaction 2h;
3) pass into N
2make protection gas, make still internal pressure maintain 0.01MPa, continue to be warming up to 180 ℃, reaction 12h;
4) continue to be warming up to 225 ℃, insulation 5h;
5) stop heating, be cooled to 120 ℃, close nitrogen, start to vacuumize, vacuum tightness and temperature are finally stabilized in 0.09MPa, 120 ℃ of left and right, stopped reaction after 2h separately;
6) be cooled to 75 ℃ with bottom discharge, obtain the sewer oil modified poly ester polyvalent alcohol (hydroxyl value 530mg KOH/g, moisture 0.06%) of liquid clear.
Claims (9)
1. utilize recovery alcohol and sewer oil to prepare a method for sewer oil modified poly ester polyvalent alcohol, it is characterized in that, comprise the following steps:
1) by low molecular polylol raw material and sewer oil and catalyzer input pet reaction still;
2) method that adopts high temperature oil bath to heat, is warming up to 140～150 ℃, reaction 1～1.5h;
3) pass into N
2make protection gas, make still internal pressure maintain 0.01MPa, continue to be warming up to 180～190 ℃, reaction 1.5～2h;
4) continue to be warming up to 220～230 ℃, insulation 4～5h;
5) stop heating, be cooled to 120 ℃, close nitrogen, start to vacuumize, vacuum tightness and temperature are finally stabilized in 0.08～0.095Mpa, 120～125 ℃ separately, react 1.5～2h, until product moisture≤0.07 o'clock stopped reaction;
6) be cooled to 75 ℃ with bottom discharge, obtain sewer oil modified poly ester polyvalent alcohol.
2. a kind of method of utilizing recovery alcohol and sewer oil to prepare sewer oil modified poly ester polyvalent alcohol according to claim 1, is characterized in that, described low molecular polylol raw material refers to recovery alcohol mixture, mainly reclaims ethylene glycol, glycerine and Diethylene Glycol.
3. a kind of method of utilizing recovery alcohol and sewer oil to prepare sewer oil modified poly ester polyvalent alcohol according to claim 1, it is characterized in that, contained two senses and polyvalent alcohols more than two senses in described low molecular polylol raw material, with the mol ratio of sewer oil be 2.0～3.5.
4. a kind of method of utilizing recovery alcohol and sewer oil to prepare sewer oil modified poly ester polyvalent alcohol according to claim 2, is characterized in that, the mass percent of the recovery glycerine in described recovery alcohol mixture is not more than 35%.
5. a kind of utilization according to claim 2 reclaimed the method that alcohol and sewer oil are prepared sewer oil modified poly ester polyvalent alcohol, it is characterized in that, described recovery alcohol mixture and the colourity of sewer oil all in 150Hazen, and are transparent liquid.
6. a kind of method of utilizing recovery alcohol and sewer oil to prepare sewer oil modified poly ester polyvalent alcohol according to claim 2, is characterized in that, the hydroxyl value scope of described recovery alcohol mixture is 1000～1250mgKOH/g.
7. a kind of method of utilizing recovery alcohol and sewer oil to prepare sewer oil modified poly ester polyvalent alcohol according to claim 1, it is characterized in that, in described recovery alcohol mixture, content is not less than 90%, and other impurity can be water, small molecules polyvalent alcohol and ester class any one or a few.
8. a kind of utilization according to claim 7 reclaimed the method that alcohol and sewer oil are prepared sewer oil modified poly ester polyvalent alcohol, it is characterized in that, described small molecules polyvalent alcohol and the molecular weight of ester class are all in 240g/mol, and boiling point is all less than 300 ℃.
9. a kind of method of utilizing recovery alcohol and sewer oil to prepare sewer oil modified poly ester polyvalent alcohol according to claim 1, is characterized in that, described catalyzer is potassium hydroxide, and accounts for 0.01～0.03% of all raw material total masses.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310655152.0A CN103820226A (en) | 2013-12-06 | 2013-12-06 | Method for preparing swill-cooked dirty oil modified polyester polyol from recovered alcohol and swill-cooked dirty oil |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201310655152.0A CN103820226A (en) | 2013-12-06 | 2013-12-06 | Method for preparing swill-cooked dirty oil modified polyester polyol from recovered alcohol and swill-cooked dirty oil |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101029119A (en) * | 2007-03-23 | 2007-09-05 | 上海中科合臣股份有限公司 | Production of recovered grease polybasic alcohol and its hard polyurethane foaming plate |
| CN101602665A (en) * | 2008-06-13 | 2009-12-16 | 郝在晨 | A kind of grease-based polyol and preparation method thereof |
| CN103275306A (en) * | 2013-05-31 | 2013-09-04 | 南京工业大学 | Method for preparing grease-based polyol through direct esterification interesterification of illegal cooking oil |
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2013
- 2013-12-06 CN CN201310655152.0A patent/CN103820226A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101029119A (en) * | 2007-03-23 | 2007-09-05 | 上海中科合臣股份有限公司 | Production of recovered grease polybasic alcohol and its hard polyurethane foaming plate |
| CN101602665A (en) * | 2008-06-13 | 2009-12-16 | 郝在晨 | A kind of grease-based polyol and preparation method thereof |
| CN103275306A (en) * | 2013-05-31 | 2013-09-04 | 南京工业大学 | Method for preparing grease-based polyol through direct esterification interesterification of illegal cooking oil |
Non-Patent Citations (1)
| Title |
|---|
| 晁国库等: "聚酯多元醇的合成方法研究", 《长春工业大学学报（自然科学版）》, vol. 28, no. 1, 31 May 2007 (2007-05-31), pages 17 - 21 * |
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Application publication date: 20140528 |