CN102432430A - Method for preparing trimethylolpropane in multi-section cyclic hydrogenation mode - Google Patents
Method for preparing trimethylolpropane in multi-section cyclic hydrogenation mode Download PDFInfo
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Abstract
The invention relates to a method for preparing trimethylolpropane in a multi-section cyclic hydrogenation mode. The method is characterized by comprising the following steps of: firstly, in a first section, contacting a condensation solution, which is obtained by condensation of formaldehyde and n-butyraldehyde, with a first type of copper (Cu) base catalyst which consists of Cu, zinc (Zn) and manganese (Mn) to make 2,2-dihydromethyl butyraldehyde and part of trimethylolpropane polymer converted into the trimethylolpropane; secondly, in a second section, contacting the condensation solution with a second type of Cu-base catalyst which consists of Cu, Zn and aluminum (Al), and performing hydrogenolysis on the reminding polymer to obtain the trimethylolpropane; and finally, after rectification, extracting a high-boiling residue such as the polymer in a residue at the bottom of a kettle, contacting the high-boiling residue with the second type of Cu-base catalyst, and then converting into the trimethylolpropane. By adoption of the method, high-selectivity and high-yield continuous production of the high-quality trimethylolpropane can be realized.
Description
Technical field
The present invention relates to the preparation method of TriMethylolPropane(TMP), specifically a kind of method of multistage circulation hydrogenation preparing TriMethylolPropane(TMP).
Technical background
3 typical methylols are arranged on the TriMethylolPropane(TMP) molecule; Thereby has the polyvalent alcohol character that is similar to glycerine; Can generate monoesters or polyester with organic acid reaction, generate acetal, ketal, generate carbamate etc. with di-isocyanate reaction with aldehyde, reactive ketone; Be a kind of broad-spectrum Organic Chemicals and Chemicals; Be mainly used in fields such as Synolac, urethane, unsaturated polyester, vibrin, coating, also can be used for synthetic aircraft oil, softening agent, tensio-active agent, wetting agent, explosive, printing-ink etc., also can directly be used as the thermo-stabilizer of textile auxiliary agent and polyvinyl chloride resin etc.
In the industry, TriMethylolPropane(TMP) is to be raw material with butyraldehyde-n and formaldehyde, and condensation reaction makes under the basic catalyst effect.Its production technique has two kinds, and a kind of is intersection Canizaro condensation method, and another kind is an aldehyde hydrogenating reduction method.
The Canizaro condensation method of intersecting is the traditional method of producing TriMethylolPropane(TMP); Chinese patent CN1263081A, CN1428323A, CN1919815A, CN101102986A etc. have related to this method; This method technology is fairly simple; Easy master does not need high temperature, high pressure and special catalyst, relatively is applicable to middle and small scale industry batch production.But this method by product is more, poor product quality, and the aftertreatment workload is bigger, and production cost is high, the product purification difficulty, China mainly adopts this method to produce with the TriMethylolPropane(TMP) manufacturer of Japan at present.
The formaldehyde utilization ratio of aldehyde hydrogenating reduction method is high, can save a large amount of formaldehyde and alkali raw material, and side reaction product is less relatively; Good product quality, purification are comparatively simple, and hydrogenation unit and catalyzer are had relatively high expectations; Manufacturing requirements is also higher; Relatively be fit to large-scale continuous production, at present more American-European major companies make in this way, and U.S. Pat 20020168980 has been described a kind of through distilling purifying from 2; The method of the TriMethylolPropane(TMP) that the hydrogenation of 2-dihydroxymethyl butyraldehyde produces, not mentioned hydrogenation process in the literary composition; The condensated liquid that adopts Ni catalyzer PARA FORMALDEHYDE PRILLS(91,95) and n butyraldehyde aldolization to produce in the Japanese Patent 2001002330 carries out the method that hydrogenation prepares TriMethylolPropane(TMP), and this method catalyst system therefor costs an arm and a leg, and is not suitable for large-scale commercial prodn; The condensated liquid that adopts CuCrO4 PARA FORMALDEHYDE PRILLS(91,95) and n butyraldehyde aldolization to produce among the patent WO9407831 carries out the method that hydrogenation prepares TriMethylolPropane(TMP); This method adopts Cu, Cr catalyzer; Catalyzer is cheap, but yield is lower, and is 72%; Fail high boiling material such as polymer are handled fully, the adding of Cr pollutes environment.
The key intermediate DMB (2,2-dihydroxymethyl butyraldehyde-n) that the aldehyde hydrogenation method prepares TMP can be prepared under base catalysis by excessive formaldehyde and butyraldehyde-n, obtains behind the DMB hydrogenation in the presence of catalyzer, and reaction mechanism is suc as formula shown in 1.
Formula 1
But in the process of preparation DMB; Inevitably have the appearance of high boiling material such as a large amount of TMP polymers; For example dimer, tripolymer, its structure be suc as formula shown in 2, their appearance be prone to bring hydrogenation not thoroughly, the appearance of problems such as separation difficulty, reduction product yield and quality.
Formula 2
Though hydrogenation method is than discrimination method tool economy, environmental protection, advantage such as efficient, the appearance of high boiling material such as polymer has reduced the productive rate of TriMethylolPropane(TMP) indirectly; Increased isolating difficulty, had influence on the quality of product, to this problem of hydrogenation method; Need improve method of hydrotreating at present; Select appropriate catalyst, high boiling material such as simultaneously effective hydrogenolysis polymer, the productive rate and the quality of raising TriMethylolPropane(TMP).
Summary of the invention
The present invention aims to provide the method for multistage circulation hydrogenation preparing TriMethylolPropane(TMP); Effective hydrogenolysis TriMethylolPropane(TMP) polymer (the for example dimer of TriMethylolPropane(TMP), tripolymer; These are called for short dimer, tripolymer in this application respectively) etc. high boiling material; Improve hydrogenation selectivity, improve the content and the purity of TriMethylolPropane(TMP) in the hydride, can obtain highly purified TriMethylolPropane(TMP) through after the simple separation.
In order to reach above purpose, technical scheme of the present invention is following:
A kind of method of multistage circulation hydrogenation preparing TriMethylolPropane(TMP), this method comprises the steps: 1) be rich in 2, the condensated liquid of 2-dihydroxymethyl butyraldehyde by formaldehyde and butyraldehyde-n condensation prepared under the effect of tertiary amine catalyst; 2) by the condensated liquid of step 1 preparation in first section tubular reactor with first kind of catalyst based contact of Cu of adding Mn and Zn, and carry out first section hydrogenation reaction with hydrogen and obtain hydride; 3) hydride in the step 2 in second section tubular reactor with second kind of catalyst based contact of Cu of adding Al and Zn, and carry out second section hydrogenation reaction with hydrogen, obtain containing the hydrogenation products of TriMethylolPropane(TMP).
In the methods of the invention, in the step 1), the mol ratio of formaldehyde and butyraldehyde-n is 2.2-4.0: 1, be preferably 2.6-3.5: 1; The add-on of tertiary amine catalyst is the 3%-10% of butyraldehyde-n molar weight, preferred 4-8%, and the temperature of condensation reaction is 30-70 ℃, and solvent is water, C1-C4 fatty alcohol; Particular methanol or ethanol or water, more preferably water, the concentration of formalin is at 10%-37%; Solvent load is 40-80wt% (based on the butyraldehyde-n quality), preferred 40-60%.At 50-100KPa, 70-100 ℃ the unreacted formaldehyde of condition recover, butyraldehyde-n and tertiary amine, make and be rich in 2 after reaction is accomplished, the polymer of 2-dihydroxy butyraldehyde and TriMethylolPropane(TMP) is the condensated liquid of high boiling material such as dimer, tripolymer for example.
Wherein, described tertiary amine catalyst is the tertiary amine of total carbon atom number in the 3-15 scope, preferably Trimethylamine 99, triethylamine, Tributylamine or dimethyl butylamine, more preferably Trimethylamine 99 or triethylamine.
In the methods of the invention, the condition of first section hydrogenation be temperature 100-120 ℃ of scope, pressure is in the 1-4MPa scope, air speed is 0.1-1.5g/mL catalyzer * min, preferred 0.5-1.0g/mL (with 2,2-dihydroxymethyl butyraldehyde quality is a benchmark).
Wherein, the hydrogen of first section hydrogenation reaction and aldehyde radical mol ratio (be in hydrogen and the condensated liquid 2, the mol ratio of the aldehyde radical of 2-dihydroxy butyraldehyde) are 10-20: 1, preferred 12-18: 1, more preferably 14-16: 1.
Wherein, be benchmark with the catalyzer total amount, first kind of catalyst based Cu that consists of of Cu accounts for 30-75%, preferred 50-70%, Mn accounts for 1-15%, preferred 3-7%, Zn accounts for 20-60%, preferred 20-30%.
In the methods of the invention, the condition of second section hydrogenation be temperature 110-140 ℃ of scope, pressure is in the 1-4MPa scope, air speed is 1.0-10.0g/mL catalyzer * min, preferred 3-7% (is benchmark with hydride quality behind first section hydrogenation).
Wherein, the hydrogen of second section hydrogenation reaction and ether mol ratio (being the mol ratio of the ether group in dimer, the tripolymer in the hydride that obtains of the hydrogen and the first step) are 10-25: 1, preferred 12-22: 1, more preferably 14-20: 1, further preferred 15-18: 1;
Wherein, be benchmark with the catalyzer total amount, second kind of catalyst based Cu that consists of of Cu accounts for the preferred 50-70% of 30-75%, and Al accounts for 1-15%, preferred 4-10%, Zn accounts for 20-60%, preferred 20-30%.
In the methods of the invention, the filling ratio of the catalyzer in the catalyzer in first section tubular reactor and the second section tubular reactor is 1: 1.1-2.5 (weight ratio), preferred 1: 1.2-1.8.
In the inventive method, the 1st) condensated liquid that obtains comprises 2,2-dihydroxymethyl butyraldehyde 18-50wt% the step; Preferred 20-35%, TriMethylolPropane(TMP) 2-4wt%, preferred 2.5-4%; Dimer 1.5-4wt%, preferred 1.5-3.0%, tripolymer 0.2-1.2wt%; Preferred 0.3-0.8%, all the other are water and impurity; The 2nd) go on foot the hydride that obtains and comprise TriMethylolPropane(TMP) 20-55wt%, preferred 23-40%, dimer 1.5-4wt%, preferred 1.5-3.0%, tripolymer 0.2-1.0-1.2wt%, preferred 0.3-0.8%, all the other are water and impurity; The 3rd) comprise TriMethylolPropane(TMP) 25-55wt% in the product that the step obtains, preferred 27%-43%, dimer 0-0.5wt%, preferred 0-0.3%, tripolymer 0.-0.15wt%, preferred 0-0.1%, all the other are water and impurity.
The inventive method also comprises step 4) and 5): 4) hydrogenation products that contains TriMethylolPropane(TMP) of step 3 output is removed solvent and rectifying obtains TriMethylolPropane(TMP); Then 5) the remaining raffinate that mainly contains dimer, tripolymer, TriMethylolPropane(TMP) extracts with organic solvent after rectifying; Extract turns back to the hydrogenation that circulates in second section tubular reactor, so that the polymer of hydrogenolysis TriMethylolPropane(TMP) is a TriMethylolPropane(TMP).The composition of the liquid after the extraction (extract) is mainly TriMethylolPropane(TMP) and its dimer, tripolymer etc.
Wherein, the condition that removes solvent be temperature 60-110 ℃ of scope, preferred 70-100 ℃ of pressure is in the 50-100KPa scope; Preferred 50-80KPa; The condition of rectifying be temperature 130-160 ℃ of scope, preferred 130-150 ℃ of pressure is in the 5-10KPa scope, preferred 5-8KPa.
Wherein, the organic solvent that extraction is used is the Fatty Alcohol(C12-C14 and C12-C18) of C1-C10, the Fatty Alcohol(C12-C14 and C12-C18) of preferred C8-C10.
Wherein, the add-on of extraction solvent is 1-2 a times of raffinate volume after the rectifying, and the extraction mode is a counter-current extraction.
Use among the present invention that first kind and second kind of Cu are catalyst based to be the Cu-Zn system; The existence of Zn helps lend some impetus to reduction fully and the dispersion of active ingredient Cu; The synergy of Cu, Zn has been improved the overall performance of catalyzer; Catalyzer is more stable; Improve activity of such catalysts and to the selectivity of aldehyde compound, can avoid aldehyde compound that the Tishchenko condensation reaction takes place simultaneously and generate ester class high boiling material, cost is low, the efficient advantages of higher having aspect the hydrogenation of aldehyde compound for the Cu-Zn System Catalyst.
The Cu of first section Cu-Zn system of filling with second section tubular reactor is catalyst based among the present invention only shows that the interpolation kind of auxiliary agent is different, has guaranteed that two kinds of Cu are catalyst based to have similar work-ing life.First section Cu-Zn catalyzer that adopts the Mn modification wherein, the further adding of Mn improves dispersion degree of active components, improves the ratio of Cu+/Cu, helps the hydrogenation of aldehyde compound; Second section Cu-Zn catalyzer that adopts the Al modification; The adding of Al helps the dispersion of Cu; Increase the specific surface of catalyzer, increase the activity of such catalysts center, change the microtexture of catalyzer; Al has both sexes simultaneously, helps to improve the Cu-Zn catalyzer to containing the polymeric hydrogenolytic cleavage of ehter bond.The catalyst based multistage circulation hydrogenation of Cu that is filled with two kinds of similar catalytic life improved the whole selectivity of hydrogenation, reduced production costs, easy to operate.
Positively effect of the present invention is:
1) TriMethylolPropane(TMP) that adopts the inventive method to obtain has productive rate up to 89～93%, and purity is high, the advantage of quality better.
2) the present invention adopts multistage circulation hydrogenation, and whole selectivity is good, and hydrogenation is thorough, after the hydrogenation in the hydrogenation high boiling material content low, be easy to isolation of trimethylolpropane, raffinate improves the production efficiency of TriMethylolPropane(TMP), environmental friendliness greatly behind the extraction cycle hydrogenation.
Description of drawings:
Accompanying drawing 1 is whole process flow sketch of the present invention
Embodiment:
Describe the present invention through the embodiment example below.Scope of the present invention is not limited to this embodiment.
Analytical conditions for gas chromatography is: the analytical instrument of employing is Agilent7820A; Chromatographic column: HP-5MS (30m * 0.25mm * 0.25 μ m); Sample introduction temperature: 280 ℃.The temperature programming condition: 50 ℃ keep 1min, and the speed with 15 ℃/min rises to 280 ℃ then, and keep 5min.Carrier gas: high pure nitrogen (purity 99.999%).Detector: fid detector, column flow rate 1ml/min, 300 ℃ of detector temperatures.
Analytical procedure: marker method, internal standard substance are tetradecane hydrocarbon.
Technological process of the present invention is following:
Condensation reaction is taking place under the effect of tertiary amine catalyst and solvent in raw material formaldehyde and butyraldehyde-n in the condensation reaction still, reaction product makes through first rectifying tower and is rich in 2, the condensated liquid of 2-dihydroxymethyl butyraldehyde; Reclaim unreacted butyraldehyde-n, formaldehyde, Trimethylamine 99 etc.; Obtain being rich in 2, the condensated liquid of 2-dihydroxymethyl butyraldehyde, condensated liquid are flowed through and are filled with first kind of first tubular reactor that Cu is catalyst based; At 100-120 ℃; Hydrogenation 2 under the condition of 1-4MPa, 2-dihydroxy butyraldehyde, and the high boiling material such as polymer of hydrogenolysis small portion TriMethylolPropane(TMP); Hydride in first tubular reactor is filled with in the second catalyst based tubular reactor of second kind of Cu by entering, at 110-140 ℃, and hydrogenation under the condition of 1-4MPa, the high boiling material such as polymer of the most hydroxymethyl-propane of hydrogenolysis; Hydride in second section carries out precipitation, separating prod TriMethylolPropane(TMP) by getting into second rectifier unit, and cauldron bottom residue is in flowing into extraction tower, and extraction solvent gets into counter-current extraction in the extraction tower; Raffinate gets into the hydrogenation that circulates in second section tubular reactor.
Embodiment one
The formalin 6226.4g of adding 15% in the 10L reaction kettle, 30% trimethylamine aqueous solution 139.2g is warming up to 40 ℃; Drip the 1018.9g butyraldehyde-n, slowly be warming up to 60 ℃ after dripping and continue reaction 2h, 70 ℃ ,-condition of 0.18MPa under the rectifying condensation reaction solution; Reclaim unreacted butyraldehyde-n, formaldehyde, Trimethylamine 99 etc.; Obtain being rich in 2, the condensated liquid of 2-dihydroxymethyl butyraldehyde, main high-boiling-point impurity is dimerization, the tripolymer of TriMethylolPropane(TMP) in the condensation.The chromatogram ration analysis condensation reaction solution; Wherein in the condensated liquid 2, the massfraction of 2-dihydroxymethyl butyraldehyde is 19.24%, and the massfraction of TriMethylolPropane(TMP) is 2.37%; Dimeric massfraction is 2.18%; Trimerical massfraction is 0.79%, impurity 1.36%, and all the other are aqueous solvent.
In first, second tubular reactor, load 120mL respectively, 144mLCu is catalyst based, wherein, first kind of catalyst based component of Cu is Cu55% in first tubular reactor; Mn2%, Zn43%, second kind of catalyst based component of Cu is Cu55% in second tubular reactor; Zn41%, Al4%, two reactor is under atmosphere of hydrogen; Slowly be warming up to 240 ℃ and carry out activation 3h, after the activation, be warming up to 100 ℃, 140 ℃ respectively; Controlling first section air speed is 0.2g/mL catalyzer * min, and hydrogen-oil ratio is 12: 1, and hydrogenation pressure is 3.5MPa; Controlling second section air speed is 5g/mL catalyzer * min, and hydrogen-oil ratio is 15: 1, and hydrogenation pressure is 4.0MPa.Through gas chromatographic analysis, the massfraction of TriMethylolPropane(TMP) is 20.87% in the hydride that makes after first section hydrogenation reaction, and dimeric massfraction is 2.07%, and trimerical massfraction is 0.69%, other 1.37%, all the other are water.
Through gas chromatographic analysis; Staple is TriMethylolPropane(TMP) and a little high boiling material in the hydride that makes after second section hydrogenation reaction; Wherein the massfraction of TriMethylolPropane(TMP) is 24.93%, and dimeric massfraction is 0.34%, and trimerical massfraction is 0.082%; Other 1.39%, all the other are water.
Above-mentioned hydride at first removes moisture under 105-110 ℃, the condition of 80-84KPa in rectifying tower, subsequently at 135-140 ℃, separate obtaining white solid TriMethylolPropane(TMP) 1733.2g under the condition of 2-6KPa from cat head; Selectivity 99.23%, productive rate are 91.41%, and gas phase purity is 99.87%; Through gas chromatographic analysis; Rectifying tower tower bottoms 134.8mL, staple is TriMethylolPropane(TMP) 19.27%, dimer 43.18%, tripolymer 30.79%, other is 6.76% years old.Speed with getting into behind the 213mL octanol counter-current extraction with 3mL/min gets into hydrogenation in second section tubular reactor.
Embodiment two
The formalin 6187.5g of adding 25% in the 10L reaction kettle, 30% trimethylamine aqueous solution 276.6g is warming up to 40 ℃; Drip the 1687.5g butyraldehyde-n, slowly be warming up to 60 ℃ after dripping and continue reaction 2h, 70 ℃ ,-condition of 0.18MPa under the rectifying condensation reaction solution; Reclaim unreacted butyraldehyde-n, formaldehyde, Trimethylamine 99 etc.; Obtain being rich in 2, the condensated liquid of 2-dihydroxymethyl butyraldehyde, main high-boiling-point impurity is dimerization, the tripolymer of TriMethylolPropane(TMP) in the condensation.The chromatogram ration analysis condensation reaction solution, wherein 2, the massfraction of 2-dihydroxymethyl butyraldehyde is 33.52%; The massfraction of TriMethylolPropane(TMP) is 2.38%, and dimeric massfraction is 3.24%, and trimerical massfraction is 0.97%; Other 1.42%, all the other are water.
In first, second tubular reactor, load 120mL respectively, 150mLCu is catalyst based, wherein, first kind of catalyst based component of Cu is Cu49% in first tubular reactor; Mn4%, Zn47%, second kind of catalyst based component of Cu is Cu48% in second tubular reactor; Zn45%, Al7%, two reactor is under atmosphere of hydrogen; Slowly be warming up to 240 ℃ and carry out activation 3h, after the activation, be warming up to 120 ℃, 130 ℃ respectively; Controlling first section air speed is 0.5g/mL catalyzer * min, and hydrogen-oil ratio is 15: 1, and hydrogenation pressure is 3.5MPa; Controlling second section air speed is 8g/mL catalyzer * min, and hydrogen-oil ratio is 20: 1, and hydrogenation pressure is 4.0MPa.Through gas chromatographic analysis, the massfraction of TriMethylolPropane(TMP) is 36.08% in the hydride that makes after first section hydrogenation reaction, and dimeric massfraction is 2.87%, and trimerical massfraction is 0.72%, other 1.39%, all the other are water.
Through gas chromatographic analysis; Staple is TriMethylolPropane(TMP) and a little high boiling material in the hydride that makes after second section hydrogenation reaction; Wherein the massfraction of TriMethylolPropane(TMP) is 36.37%, and dimeric massfraction is 0.39%, and trimerical massfraction is 0.12%; Other 1.38%, all the other are water.
Above-mentioned hydride at first removes moisture under 105-110 ℃, the condition of 80-84KPa; At 135-140 ℃, obtain white solid TriMethylolPropane(TMP) 2916.4g from the cat head separation under the condition of 2-6KPa subsequently, selectivity is 99.18%; Yield is 92.87%, and gas phase purity is 99.83%.Rectifying tower tower bottoms 157.6mL; Through gas chromatographic analysis; Staple is TriMethylolPropane(TMP) 20.41%, dimer 45.04%, tripolymer 30.52%, other 4.03%, get into hydrogenation in second section tubular reactor with the speed that gets into behind the 280mL octanol counter-current extraction with 3mL/min.
Embodiment three
The formalin 4816.8g of adding 37% in the 10L reaction kettle, 30% trimethylamine aqueous solution 302.4g is warming up to 40 ℃; Drip the 1944.5g butyraldehyde-n, slowly be warming up to 60 ℃ after dripping and continue reaction 2h, 70 ℃ ,-condition of 0.18MPa under the rectifying condensation reaction solution; Reclaim unreacted butyraldehyde-n, formaldehyde, Trimethylamine 99 etc.; Obtain being rich in 2, the condensated liquid of 2-dihydroxymethyl butyraldehyde, main high-boiling-point impurity is dimerization, the tripolymer of TriMethylolPropane(TMP) in the condensation.The chromatogram ration analysis condensation reaction solution, wherein 2, the massfraction of 2-dihydroxymethyl butyraldehyde is 43.17%; The massfraction of TriMethylolPropane(TMP) is 2.61%, and dimeric massfraction is 3.97%, and trimerical massfraction is 1.16%; Other 1.42%, all the other are water.
In first, second tubular reactor, load 120mL respectively, 160mLCu is catalyst based, wherein, first kind of catalyst based component of Cu is Cu65% in first tubular reactor; Mn12%, Zn23%, second kind of catalyst based component of Cu is Cu66% in second tubular reactor; Zn23%, Al11%, two reactor is under atmosphere of hydrogen; Slowly be warming up to 240 ℃ and carry out activation 3h, after the activation, be warming up to 110 ℃, 120 ℃ respectively; Controlling first section air speed is 0.8g/mL catalyzer * min, and hydrogen-oil ratio is 20: 1, and hydrogenation pressure is 4.0MPa; Controlling second section air speed is 3g/mL catalyzer * min, and hydrogen-oil ratio is 25: 1, and hydrogenation pressure is 4.0MPa.Through gas chromatographic analysis, the massfraction of TriMethylolPropane(TMP) is 46.08% in the hydride that makes after first section hydrogenation reaction, and dimeric massfraction is 3.87%, and trimerical massfraction is 1.12%, other 1.39%, all the other are water.
Through gas chromatographic analysis; Staple is TriMethylolPropane(TMP) and a little high boiling material in the hydride that makes after second section hydrogenation reaction; Wherein the massfraction of TriMethylolPropane(TMP) is 48.37%, and dimeric massfraction is 0.49%, and trimerical massfraction is 0.13%; Other 1.44%, all the other are water.
Above-mentioned hydride at first removes moisture under 105-110 ℃, the condition of 80-84KPa; At 135-140 ℃, obtain white solid TriMethylolPropane(TMP) 3285.9g from the cat head separation under the condition of 2-6KPa subsequently, selectivity is 99.27%; Yield is 90.74%, and gas phase purity is 99.78%.Rectifying tower tower bottoms 164.5mL; Through gas chromatographic analysis; Staple is TriMethylolPropane(TMP) 21.35%, dimer 44.26%, tripolymer 29.83%, other 4.56%, get into hydrogenation in second section tubular reactor with the speed that gets into behind the 300mL octanol counter-current extraction with 3mL/min.
Claims (14)
1. the method for a multistage circulation hydrogenation preparing TriMethylolPropane(TMP), this method comprises the steps:
1) is rich in 2, the condensated liquid of 2-dihydroxymethyl butyraldehyde by formaldehyde and butyraldehyde-n condensation prepared under the effect of tertiary amine catalyst; 2) by the condensated liquid of step 1 preparation in first section tubular reactor with first kind of catalyst based contact of Cu of adding Mn and Zn, and carry out first section hydrogenation reaction with hydrogen and obtain hydride; 3) hydride in the step 2 in second section tubular reactor with second kind of catalyst based contact of Cu of adding Al and Zn, and carry out second section hydrogenation reaction with hydrogen, obtain containing the hydrogenation products of TriMethylolPropane(TMP).
2. according to the method for claim 1, it is characterized in that; In the step 1); The mol ratio of formaldehyde and butyraldehyde-n is 2.2-4.0: 1, and the add-on of tertiary amine catalyst is the 3%-10% of butyraldehyde-n molar weight, the temperature of condensation reaction is 30-70 ℃; Solvent is water, C1-C4 fatty alcohol, and solvent load is 40-80wt% (based on the butyraldehyde-n quality).
3. according to the method for claim 2, it is characterized in that; Described tertiary amine catalyst is the tertiary amine of total carbon atom number in the 3-15 scope, preferably Trimethylamine 99, triethylamine, Tributylamine or dimethyl butylamine.
4. according to each described method among the claim 1-3, it is characterized in that; The condition of first section hydrogenation be temperature 100-120 ℃ of scope, pressure is in the 1-4MPa scope, air speed is 0.1-1.5g/mL catalyzer * min (with 2,2-dihydroxymethyl butyraldehyde quality is a benchmark).
5. method according to claim 4 is characterized in that; The mol ratio of first section hydrogenation reaction hydrogen and aldehyde radical is 10-20: 1, preferred 12-18: 1.
6. method according to claim 5 is characterized in that; With the catalyzer total amount is benchmark, and first kind of catalyst based Cu that consists of of Cu accounts for 30-75%, and Mn accounts for 1-15%, and Zn accounts for 20-60%.
7. according to each described method among the claim 1-6, it is characterized in that; The condition of second section hydrogenation be temperature 110-140 ℃ of scope, pressure is in the 1-4MPa scope, air speed is 1.0-10.0g/mL catalyzer * min (is benchmark with hydride quality behind first section hydrogenation).
8. method according to claim 7 is characterized in that; The hydrogen of second section hydrogenation reaction and ether mol ratio are 10-25: 1, preferred 12-22: 1.
9. method according to claim 8 is characterized in that; With the catalyzer total amount is benchmark, and second kind of catalyst based Cu that consists of of Cu accounts for 30-75%, and Al accounts for 1-15%, and Zn accounts for 20-60%.
10. according to each described method of claim 1-9, it is characterized in that; The filling ratio of the catalyzer in the catalyzer in first section tubular reactor and the second section tubular reactor is 1: 1.15-1.5.
11. according to each described method among the claim 1-10; It is characterized in that also comprising step 4) and 5): 4) hydrogenation products that contains TriMethylolPropane(TMP) of step 3 output is removed solvent and rectifying obtains TriMethylolPropane(TMP); Then 5) the remaining raffinate that mainly contains dimer, tripolymer, TriMethylolPropane(TMP) extracts with organic solvent after rectifying, and extract turns back to the hydrogenation that circulates in second section tubular reactor.
12. the method according to claim 11 is characterized in that; The condition that removes solvent be temperature 60-110 ℃ of scope, pressure is in the 50-100KPa scope, the condition of rectifying be temperature 130-160 ℃ of scope, pressure is in the 5-10KPa scope.
13. the method according to claim 12 is characterized in that; The organic solvent that extraction is used is the Fatty Alcohol(C12-C14 and C12-C18) of C1-C10, the Fatty Alcohol(C12-C14 and C12-C18) of preferred C8-C10.
14. the method according to claim 13 is characterized in that; The add-on of extraction solvent is 1-2 a times of raffinate volume after the rectifying, and the extraction mode is a counter-current extraction.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103254034A (en) * | 2013-05-22 | 2013-08-21 | 烟台万华聚氨酯股份有限公司 | Trimethylolpropane preparation method |
| CN103274899A (en) * | 2013-05-22 | 2013-09-04 | 烟台万华聚氨酯股份有限公司 | Preparation method of trimethylolpropane |
| CN104140358A (en) * | 2014-07-28 | 2014-11-12 | 万华化学集团股份有限公司 | Method for preparing trimethylolpropane through hydrogenation |
| CN104892364A (en) * | 2015-06-02 | 2015-09-09 | 万华化学集团股份有限公司 | Method for preparing trimethylolpropane by adopting hydrogenation method |
| KR20190041195A (en) * | 2017-10-12 | 2019-04-22 | 주식회사 엘지화학 | Preparing method of dimethylolbutanal and preparation method of trimethylolpropane using the same |
| CN112517018A (en) * | 2020-11-30 | 2021-03-19 | 万华化学集团股份有限公司 | Catalyst for preparing trimethylolpropane by hydrogenating 2, 2-dimethylolbutyraldehyde and preparation method and application thereof |
| CN116874349A (en) * | 2023-07-06 | 2023-10-13 | 万华化学集团股份有限公司 | Method for preparing 2, 2-dimethylolbutyraldehyde and trimethylolpropane |
| RU2819814C1 (en) * | 2023-07-17 | 2024-05-24 | Федеральное государственное бюджетное учреждение науки Институт геологии и геохимии им. академика А.Н. Заварицкого Уральского отделения Российской академии наук | Method of producing single-phase zircon |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103274899A (en) * | 2013-05-22 | 2013-09-04 | 烟台万华聚氨酯股份有限公司 | Preparation method of trimethylolpropane |
| CN103254034A (en) * | 2013-05-22 | 2013-08-21 | 烟台万华聚氨酯股份有限公司 | Trimethylolpropane preparation method |
| CN103254034B (en) * | 2013-05-22 | 2015-09-16 | 万华化学集团股份有限公司 | A kind of preparation method of TriMethylolPropane(TMP) |
| CN103274899B (en) * | 2013-05-22 | 2015-09-16 | 万华化学集团股份有限公司 | A kind of preparation method of TriMethylolPropane(TMP) |
| CN104140358B (en) * | 2014-07-28 | 2015-11-25 | 万华化学集团股份有限公司 | A kind of hydrogenation method prepares the method for TriMethylolPropane(TMP) |
| CN104140358A (en) * | 2014-07-28 | 2014-11-12 | 万华化学集团股份有限公司 | Method for preparing trimethylolpropane through hydrogenation |
| CN104892364A (en) * | 2015-06-02 | 2015-09-09 | 万华化学集团股份有限公司 | Method for preparing trimethylolpropane by adopting hydrogenation method |
| KR20190041195A (en) * | 2017-10-12 | 2019-04-22 | 주식회사 엘지화학 | Preparing method of dimethylolbutanal and preparation method of trimethylolpropane using the same |
| KR102359896B1 (en) * | 2017-10-12 | 2022-02-07 | 주식회사 엘지화학 | Preparing method of dimethylolbutanal and preparation method of trimethylolpropane using the same |
| CN112517018A (en) * | 2020-11-30 | 2021-03-19 | 万华化学集团股份有限公司 | Catalyst for preparing trimethylolpropane by hydrogenating 2, 2-dimethylolbutyraldehyde and preparation method and application thereof |
| CN112517018B (en) * | 2020-11-30 | 2022-08-05 | 万华化学集团股份有限公司 | Catalyst for preparing trimethylolpropane by hydrogenating 2, 2-dimethylolbutyraldehyde and preparation method and application thereof |
| CN116874349A (en) * | 2023-07-06 | 2023-10-13 | 万华化学集团股份有限公司 | Method for preparing 2, 2-dimethylolbutyraldehyde and trimethylolpropane |
| RU2819814C1 (en) * | 2023-07-17 | 2024-05-24 | Федеральное государственное бюджетное учреждение науки Институт геологии и геохимии им. академика А.Н. Заварицкого Уральского отделения Российской академии наук | Method of producing single-phase zircon |
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