CN102432430B - Method for preparing trimethylolpropane in multi-section cyclic hydrogenation - Google Patents
Method for preparing trimethylolpropane in multi-section cyclic hydrogenation 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 preparing trimethylolpropane in multi-section cyclic hydrogenation mode.
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, with aldehyde, reactive ketone generates acetal, ketal, generate carbamate etc. with di-isocyanate reaction, a kind of broad-spectrum Organic Chemicals and Chemicals, be mainly used in Synolac, urethane, unsaturated polyester, vibrin, the fields such as 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.
Industrial, TriMethylolPropane(TMP) is that condensation reaction makes under the basic catalyst effect take butyraldehyde-n and formaldehyde as raw material.Its production technique has two kinds, and a kind of is intersection Canizaro condensation method, and another kind is 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 technique is fairly simple, easily grasp, do not need high temperature, high pressure and special catalyst, relatively be applicable to middle and small scale industry batch production.But this method by product is more, poor product quality, and the aftertreatment workload is larger, and production cost is high, product purification difficulty, the TriMethylolPropane(TMP) manufacturer of China and Japan mainly adopts this method to produce at present.
The formaldehyde utilization ratio of aldehyde hydrogenating reduction method is high, can save a large amount of formaldehyde and alkali raw material, side reaction product is relatively less, good product quality, purification is comparatively simple, hydrogenation unit and catalyzer are had relatively high expectations, manufacturing requirements is also higher, relatively be fit to large-scale serialization production, at present more American-European major companies make in this way, US Patent No. 20020168980 has been described a kind of method of coming the TriMethylolPropane(TMP) that purifying produces from the hydrogenation of 2,2-dihydroxymethyl butyraldehyde by distillation, not mentioned hydrogenation process in literary composition; The condensated liquid that adopts Ni catalyzer PARA FORMALDEHYDE PRILLS(91,95) and n butyraldehyde aldolization to produce in Japanese Patent 2001002330 carries out the method that hydrogenation prepares TriMethylolPropane(TMP), and this method used catalyst is expensive, is not suitable for large-scale commercial production; The condensated liquid that adopts CuCrO4 PARA FORMALDEHYDE PRILLS(91,95) and n butyraldehyde aldolization to produce in 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 be 72%, fail the high boiling material such as polymer are processed fully, Cr adds 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 after DMB hydrogenation under catalyzer exists, and reaction mechanism as shown in Equation 1.
Formula 1
But in the process of preparation DMB, inevitably have the appearance of the high boiling material such as a large amount of TMP polymers, for example dimer, tripolymer, its structure as shown in Equation 2, their appearance easily bring hydrogenation not thoroughly, the appearance of the problems such as separation difficulty, reduction product yield and quality.
Formula 2
Though hydrogenation method is than discrimination method tool economy, environmental protection, the advantage such as efficient, but the appearance of the high boiling material such as polymer, indirectly reduced the productive rate of TriMethylolPropane(TMP), increase the difficulty of separating, had influence on the quality of product, for this problem of hydrogenation method, need to improve method of hydrotreating at present, select suitable catalyzer, the high boiling material such as simultaneously effective hydrogenolysis polymer, productive rate and the quality of raising TriMethylolPropane(TMP).
Summary of the invention
The present invention aims to provide the method for preparing trimethylolpropane in multi-section cyclic hydrogenation mode, effective hydrogenolysis TriMethylolPropane(TMP) polymer (for example dimer of TriMethylolPropane(TMP), tripolymer, these are called for short respectively dimer, tripolymer in this application) etc. high boiling material, improve hydrogenation selectivity, improve content and the purity of TriMethylolPropane(TMP) in hydride, can obtain highly purified TriMethylolPropane(TMP) through after simple separation.
In order to reach above purpose, technical scheme of the present invention is as follows:
A kind of method of preparing trimethylolpropane in multi-section cyclic hydrogenation mode, the method comprises the steps: 1) condensation under the effect of tertiary amine catalyst prepares the condensated liquid that is rich in 2,2-dihydroxymethyl butyraldehyde by formaldehyde and butyraldehyde-n; 2) by the condensated liquid of step 1 preparation in the first paragraph tubular reactor with catalyst based contact of the first Cu of adding Mn and Zn, and carry out the first paragraph hydrogenation reaction with hydrogen and obtain hydride; 3) hydride in step 2 in the second segment tubular reactor with catalyst based contact of the second Cu of adding Al and Zn, and carry out the second segment hydrogenation reaction with hydrogen, obtain containing the hydrogenation products of TriMethylolPropane(TMP).
In the methods of the invention, step 1) in, the mol ratio of formaldehyde and butyraldehyde-n is 2.2-4.0: 1, be preferably 2.6-3.5: 1, and the add-on of tertiary amine catalyst is the 3%-10% of butyraldehyde-n molar weight, preferred 4-8%, the temperature of condensation reaction is 30-70 ℃, 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%.Reclaim unreacted formaldehyde, butyraldehyde-n and tertiary amine after reaction is completed under the condition of 50-100KPa, 70-100 ℃, make the condensated liquid of the high boiling material such as dimer, tripolymer of polymer that is rich in 2,2-dihydroxy butyraldehyde and TriMethylolPropane(TMP).
Wherein, described tertiary amine catalyst be total carbon atom number at the tertiary amine of 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 paragraph 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 (being benchmark with 2,2-dihydroxymethyl butyraldehyde quality).
Wherein, the hydrogen of first paragraph hydrogenation reaction and aldehyde radical mol ratio (be in hydrogen and 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, take the catalyzer total amount as benchmark, the Cu that consists of that the first Cu is catalyst based accounts for 30-75%, preferred 50-70%, and 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 segment 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% (the hydride quality is as benchmark after the first paragraph hydrogenation).
Wherein, the hydrogen of second segment hydrogenation reaction and ether mol ratio (being the mol ratio of the ether group in dimer, tripolymer in the hydride that obtains of hydrogen and the first step) are 10-25: 1, preferred 12-22: 1, more preferably 14-20: 1, further preferred 15-18: 1;
Wherein, take the catalyzer total amount as benchmark, the Cu that consists of that the second Cu is catalyst based accounts for the preferred 50-70% of 30-75%, and Al accounts for 1-15%, preferred 4-10%, and Zn accounts for 20-60%, preferred 20-30%.
In the methods of the invention, the filling proportion of the catalyzer in the catalyzer in the first paragraph tubular reactor and second segment tubular reactor is 1: 1.1-2.5 (weight ratio), preferred 1: 1.2-1.8.
In the inventive method, the 1st) go on foot the condensated liquid that obtains and comprise 2,2-dihydroxymethyl butyraldehyde 18-50wt%, 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 carried out desolvation 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 the second segment tubular reactor, so that the polymer of hydrogenolysis TriMethylolPropane(TMP) is TriMethylolPropane(TMP).The composition of the liquid after extraction (extract) is mainly TriMethylolPropane(TMP) and its dimer, tripolymer etc.
Wherein, the condition of desolvation 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 of extraction use 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 times of raffinate volume after rectifying, and the extraction mode is counter-current extraction.
Use in the present invention that the first and the second Cu are catalyst based is 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, the activity of raising catalyzer reaches the selectivity to aldehyde compound, can avoid simultaneously aldehyde compound that the Tishchenko condensation reaction occurs 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 the Cu-Zn system that in the present invention, first paragraph and second segment tubular reactor are filled is catalyst based 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.Wherein first paragraph adopts the Cu-Zn catalyzer of Mn modification, and Mn further adds the dispersity that improves active ingredient, and the ratio of raising Cu+/Cu is conducive to the hydrogenation of aldehyde compound; Second segment adopts the Cu-Zn catalyzer of Al modification, Al adds the dispersion that helps Cu, increase the specific surface of catalyzer, increase the active centre of catalyzer, 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 multi-section 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 the multi-section circulation hydrogenation, and whole selectivity is good, and hydrogenation is thorough, after hydrogenation in hydrogenation high boiling material content low, be easy to isolation of trimethylolpropane, raffinate improves the production efficiency of TriMethylolPropane(TMP), environmental friendliness greatly after the extraction cycle hydrogenation.
Description of drawings:
Accompanying drawing 1 is the whole process flow diagram of the present invention
Embodiment:
Describe the present invention below by the embodiment example.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 then the speed with 15 ℃/min rises to 280 ℃, 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 as follows:
Condensation reaction is occuring 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 the 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 is flowed through and is filled with the first catalyst based tubular reactor of the first Cu, at 100-120 ℃, under the condition of 1-4MPa, hydrogenation 2,2-dihydroxy butyraldehyde, and the high boiling material such as polymer of hydrogenolysis small portion TriMethylolPropane(TMP); Hydride in the first tubular reactor is filled with in the second catalyst based tubular reactor of the second 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 segment carries out precipitation, product separation TriMethylolPropane(TMP) by entering the second rectifier unit, and cauldron bottom residue is in flowing into extraction tower, and extraction solvent enters counter-current extraction in extraction tower; Raffinate enters the hydrogenation that circulates in the second segment tubular reactor.
Embodiment one
Add 15% formalin 6226.4g in the 10L reactor, 30% trimethylamine aqueous solution 139.2g, be warming up to 40 ℃, drip the 1018.9g butyraldehyde-n, drip and slowly be warming up to 60 ℃ and continue reaction 2h afterwards, 70 ℃ ,-condition of 0.18MPa under the rectifying condensation reaction solution, reclaim unreacted butyraldehyde-n, formaldehyde, Trimethylamine 99 etc., obtain being rich in the condensated liquid of 2,2-dihydroxymethyl butyraldehyde, in condensation, main high-boiling-point impurity is dimerization, the tripolymer of TriMethylolPropane(TMP).The chromatogram ration analysis condensation reaction solution, wherein in condensated liquid 2, the massfraction of 2-dihydroxymethyl butyraldehyde is 19.24%, 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.
Load 120mL respectively in first, second tubular reactor, 144mLCu is catalyst based, wherein, in the first tubular reactor, the catalyst based component of the first Cu is Cu55%, Mn2%, Zn43%, in the second tubular reactor, the catalyst based component of the second Cu is Cu55%, Zn41%, Al4%, two reactor is under atmosphere of hydrogen, slowly be warming up to 240 ℃ and activate 3h, after activation, be warming up to respectively 100 ℃, 140 ℃, controlling the first paragraph air speed is 0.2g/mL catalyzer * min, hydrogen-oil ratio is 12: 1, and hydrogenation pressure is 3.5MPa; Controlling the second segment air speed is 5g/mL catalyzer * min, and hydrogen-oil ratio is 15: 1, and hydrogenation pressure is 4.0MPa.By gas chromatographic analysis, in the hydride that makes after the first paragraph hydrogenation reaction, the massfraction of TriMethylolPropane(TMP) is 20.87%, and dimeric massfraction is 2.07%, and trimerical massfraction is 0.69%, other 1.37%, all the other are water.
By gas chromatographic analysis, in the hydride that makes after the second segment hydrogenation reaction, main component is TriMethylolPropane(TMP) and a little high boiling material, wherein the massfraction of TriMethylolPropane(TMP) is 24.93%, dimeric massfraction is 0.34%, trimerical massfraction is 0.082%, other 1.39%, all the other are water.
At first above-mentioned hydride removes moisture under 105-110 ℃, the condition of 80-84KPa in rectifying tower, subsequently at 135-140 ℃, separate from tower top under the condition of 2-6KPa and obtain white solid TriMethylolPropane(TMP) 1733.2g, selectivity 99.23%, productive rate are 91.41%, and gas phase purity is 99.87%, by gas chromatographic analysis, rectifying tower tower bottoms 134.8mL, main component is TriMethylolPropane(TMP) 19.27%, dimer 43.18%, tripolymer 30.79%, other is 6.76% years old.Enter hydrogenation in the second segment tubular reactor with the speed that enters with 3mL/min after 213mL octanol counter-current extraction.
Embodiment two
Add 25% formalin 6187.5g in the 10L reactor, 30% trimethylamine aqueous solution 276.6g, be warming up to 40 ℃, drip the 1687.5g butyraldehyde-n, drip and slowly be warming up to 60 ℃ and continue reaction 2h afterwards, 70 ℃ ,-condition of 0.18MPa under the rectifying condensation reaction solution, reclaim unreacted butyraldehyde-n, formaldehyde, Trimethylamine 99 etc., obtain being rich in the condensated liquid of 2,2-dihydroxymethyl butyraldehyde, in condensation, main high-boiling-point impurity is dimerization, the tripolymer of TriMethylolPropane(TMP).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.
Load 120mL respectively in first, second tubular reactor, 150mLCu is catalyst based, wherein, in the first tubular reactor, the catalyst based component of the first Cu is Cu49%, Mn4%, Zn47%, in the second tubular reactor, the catalyst based component of the second Cu is Cu48%, Zn45%, Al7%, two reactor is under atmosphere of hydrogen, slowly be warming up to 240 ℃ and activate 3h, after activation, be warming up to respectively 120 ℃, 130 ℃, controlling the first paragraph air speed is 0.5g/mL catalyzer * min, hydrogen-oil ratio is 15: 1, and hydrogenation pressure is 3.5MPa; Controlling the second segment air speed is 8g/mL catalyzer * min, and hydrogen-oil ratio is 20: 1, and hydrogenation pressure is 4.0MPa.By gas chromatographic analysis, in the hydride that makes after the first paragraph hydrogenation reaction, the massfraction of TriMethylolPropane(TMP) is 36.08%, and dimeric massfraction is 2.87%, and trimerical massfraction is 0.72%, other 1.39%, all the other are water.
By gas chromatographic analysis, in the hydride that makes after the second segment hydrogenation reaction, main component is TriMethylolPropane(TMP) and a little high boiling material, wherein the massfraction of TriMethylolPropane(TMP) is 36.37%, dimeric massfraction is 0.39%, trimerical massfraction is 0.12%, other 1.38%, all the other are water.
At first above-mentioned hydride removes moisture under 105-110 ℃, the condition of 80-84KPa, at 135-140 ℃, separate obtaining white solid TriMethylolPropane(TMP) 2916.4g under the condition of 2-6KPa from tower top subsequently, selectivity is 99.18%, yield is 92.87%, and gas phase purity is 99.83%.Rectifying tower tower bottoms 157.6mL, by gas chromatographic analysis, main component is TriMethylolPropane(TMP) 20.41%, dimer 45.04%, tripolymer 30.52%, other 4.03%, enter hydrogenation in the second segment tubular reactor with the speed that enters with 3mL/min after 280mL octanol counter-current extraction.
Embodiment three
Add 37% formalin 4816.8g in the 10L reactor, 30% trimethylamine aqueous solution 302.4g, be warming up to 40 ℃, drip the 1944.5g butyraldehyde-n, drip and slowly be warming up to 60 ℃ and continue reaction 2h afterwards, 70 ℃ ,-condition of 0.18MPa under the rectifying condensation reaction solution, reclaim unreacted butyraldehyde-n, formaldehyde, Trimethylamine 99 etc., obtain being rich in the condensated liquid of 2,2-dihydroxymethyl butyraldehyde, in condensation, main high-boiling-point impurity is dimerization, the tripolymer of TriMethylolPropane(TMP).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.
Load 120mL respectively in first, second tubular reactor, 160mLCu is catalyst based, wherein, in the first tubular reactor, the catalyst based component of the first Cu is Cu65%, Mn12%, Zn23%, in the second tubular reactor, the catalyst based component of the second Cu is Cu66%, Zn23%, Al11%, two reactor is under atmosphere of hydrogen, slowly be warming up to 240 ℃ and activate 3h, after activation, be warming up to respectively 110 ℃, 120 ℃, controlling the first paragraph air speed is 0.8g/mL catalyzer * min, hydrogen-oil ratio is 20: 1, and hydrogenation pressure is 4.0MPa; Controlling the second segment air speed is 3g/mL catalyzer * min, and hydrogen-oil ratio is 25: 1, and hydrogenation pressure is 4.0MPa.By gas chromatographic analysis, in the hydride that makes after the first paragraph hydrogenation reaction, the massfraction of TriMethylolPropane(TMP) is 46.08%, and dimeric massfraction is 3.87%, and trimerical massfraction is 1.12%, other 1.39%, all the other are water.
By gas chromatographic analysis, in the hydride that makes after the second segment hydrogenation reaction, main component is TriMethylolPropane(TMP) and a little high boiling material, wherein the massfraction of TriMethylolPropane(TMP) is 48.37%, dimeric massfraction is 0.49%, trimerical massfraction is 0.13%, other 1.44%, all the other are water.
At first above-mentioned hydride removes moisture under 105-110 ℃, the condition of 80-84KPa, at 135-140 ℃, separate obtaining white solid TriMethylolPropane(TMP) 3285.9g under the condition of 2-6KPa from tower top subsequently, selectivity is 99.27%, yield is 90.74%, and gas phase purity is 99.78%.Rectifying tower tower bottoms 164.5mL, by gas chromatographic analysis, main component is TriMethylolPropane(TMP) 21.35%, dimer 44.26%, tripolymer 29.83%, other 4.56%, enter hydrogenation in the second segment tubular reactor with the speed that enters with 3mL/min after 300mL octanol counter-current extraction.
Claims (14)
1. the method for a preparing trimethylolpropane in multi-section cyclic hydrogenation mode, the method comprises the steps: 1) by formaldehyde and butyraldehyde-n condensation preparation under the effect of tertiary amine catalyst be rich in the condensated liquid of 2,2-dihydroxymethyl butyraldehyde; 2) by the condensated liquid of step 1 preparation in the first paragraph tubular reactor with catalyst based contact of the first Cu of adding Mn and Zn, and carry out the first paragraph hydrogenation reaction with hydrogen and obtain hydride; 3) hydride in step 2 in the second segment tubular reactor with catalyst based contact of the second Cu of adding Al and Zn, and carry out the second segment hydrogenation reaction with hydrogen, obtain containing the hydrogenation products of TriMethylolPropane(TMP); Wherein, take the catalyzer total amount as benchmark, the Cu that consists of that the first Cu is catalyst based accounts for 30-75%, and Mn accounts for 1-15%, and Zn accounts for 20-60%.
2. according to claim 1 method, is characterized in that; In 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 claim 2 method, is characterized in that; Described tertiary amine catalyst is that total carbon atom number is at the tertiary amine of 3-15 scope.
4. method according to claim 3, is characterized in that; The condition of first paragraph hydrogenation be temperature 100-120 ℃ of scope, pressure is in the 1-4MPa scope, air speed is 0.1-1.5g/mL catalyzer * min, is benchmark with 2,2-dihydroxymethyl butyraldehyde quality.
5. method according to claim 4, is characterized in that; The mol ratio of first paragraph hydrogenation reaction hydrogen and aldehyde radical is 10-20:1.
6. method according to claim 5, is characterized in that; The condition of second segment hydrogenation be temperature 110-140 ℃ of scope, pressure is in the 1-4MPa scope, air speed is 1.0-10.0g/mL catalyzer * min, the hydride quality is as benchmark after the first paragraph hydrogenation.
7. method according to claim 6, is characterized in that; The hydrogen of second segment hydrogenation reaction and ether mol ratio are 10-25:1.
8. method according to claim 7, is characterized in that; The hydrogen of second segment hydrogenation reaction and ether mol ratio are 12-22:1.
9. method according to claim 7, is characterized in that; Take the catalyzer total amount as benchmark, the Cu that consists of that the second Cu is catalyst based accounts for 30-75%, and Al accounts for 1-15%, and Zn accounts for 20-60%.
10. according to claim 1-9 described methods of any one, is characterized in that; The filling proportion of the catalyzer in the catalyzer in the first paragraph tubular reactor and second segment tubular reactor is 1:1.15-1.5.
11. method according to claim 10 is characterized in that; Also comprise step 4) and 5): 4) hydrogenation products that contains TriMethylolPropane(TMP) of step 3 output is carried out desolvation 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 the second segment tubular reactor.
12. method according to claim 11 is characterized in that; The condition of desolvation 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. method according to claim 12 is characterized in that; The organic solvent of extraction use is the Fatty Alcohol(C12-C14 and C12-C18) of C1-C10.
14. method according to claim 13 is characterized in that; The add-on of extraction solvent is 1-2 times of raffinate volume after rectifying, and the extraction mode is counter-current extraction.
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| 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) |
| CN104892364B (en) * | 2015-06-02 | 2016-06-01 | 万华化学集团股份有限公司 | A kind of method adopting hydrogenation method to prepare TriMethylolPropane(TMP) |
| KR102359896B1 (en) * | 2017-10-12 | 2022-02-07 | 주식회사 엘지화학 | Preparing method of dimethylolbutanal and preparation method of trimethylolpropane using the same |
| 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 |
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| CN1671640A (en) * | 2002-07-26 | 2005-09-21 | 巴斯福股份公司 | Method for increasing yield in the production of polyvalent alcohols by splitting by-products containing acetal |
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| GB8613354D0 (en) * | 1986-06-03 | 1986-07-09 | Davy Mckee Ltd | Process |
| FI109993B (en) * | 1999-07-02 | 2002-11-15 | Neste Chemicals Oy | A process for preparing polyols |
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