CN106278817A - A kind of method that continuous condensating hydrogenation method prepares trimethylolethane - Google Patents
A kind of method that continuous condensating hydrogenation method prepares trimethylolethane Download PDFInfo
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- CN106278817A CN106278817A CN201610696961.XA CN201610696961A CN106278817A CN 106278817 A CN106278817 A CN 106278817A CN 201610696961 A CN201610696961 A CN 201610696961A CN 106278817 A CN106278817 A CN 106278817A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
- C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
- C07C45/75—Reactions with formaldehyde
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C45/82—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
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Abstract
The present invention relates to a kind of method that hydrogenation method prepares trimethylolethane, wherein comprise impact flow reactor and realize the condensation reaction still of continuous aldol additive reaction and gas-liquid-solid three-phase trickle bed hydrogenation reactor and bubble type Bed hydrogenation reactor, two hydrogenation reactor serial operations, are respectively provided with New Nickel series hydrocatalyst and key component is copper chromium zinc aluminate catalyst.Percussion flow aldol reaction device ensures that formaldehyde, propionic aldehyde stably generate 2 under organic weak base continuously, 2 dihydroxymethyl propionic aldehyde intermediums, reduce the generation of by-product, there is conversion ratio high under the conditions of the hydrogenation reaction preferred process of two sections of different structures, flow process is simple, product purity is high, and the advantages such as high-temperature stability is good, the ultimate yield of trimethylolethane is up to more than 95%.
Description
Technical field
The present invention relates to quasi-east coal chemical industrial waste water processing technology field, prepare more particularly to a kind of continuous condensating hydrogenation method
The method of trimethylolethane.
Background technology
The most domestic have some to prepare some documents of polyhydric alcohol about hydrogenation method, and current domestic aldehydes, esters etc. are each
The production of class hydrogenation catalyst is the most ripe, but hydrogenation polyhydric alcohol aspect does not also have enterprise's starting apparatus and industrialization, adds
Hydrogen technique is the highest to equipment requirements.The selectivity of process safety and raw material is all had a great impact, at present by the structure of equipment
Some patents mostly to describe the Hydrogenation about polyhydric alcohol standby, but all do not have to solve some industrial problems.All
It is merely resting on the small test stage.
Patent CN104140358 mainly describes the Hydrogenation problem for trimethylolpropane process DMB esters hydrogenolysis, implements
Case is the preparation of hydrogenation catalyst, and other problems seldom relates to, and patent CN102432430 mainly describes solution hydrogenation
Method is condensed dimer and the problem of trimer that the stage generates during preparing trimethylolpropane, but condensation catalyst selects
Suitable organic weak base will solve this problem greatly.
The preparation method of the trimethylolethane of Jiangsu clear spring chemistry application mainly describes the preparation of hydrogenation catalyst.Specially
What profit CN103351277 mainly described is that Hydrogenation is for the optimization of catalyst during neopentyl glycol.
It is the most domestic that not have a mechanism or enterprise that prepared by hydrogenation method polyol process the most continuous
Production, this law explanation be that the equipment to whole technological process is designed, to technological process repeatedly groped transformation, in
1 year as long as grope and solve various industrial problem and produce qualified trimethylolethane is carried out on electricity testing device.
Trimethylolethane (TME) is a kind of unique multi-functional neopentane with three high response hydroxyls
Structure polyhydric alcohol.Application includes powder coating resin, high solid resin, alkyd resin, polyester and the production of reducibility resin.
TME can also be used for TiO 2 pigment, organic-silicon-modified polyester resin, polyurethane, epoxy resin, syntholube, plasticising
Agent, ink, photographic chemistry product and adhesive.Neopentane structure is provided that the stability of excellence, improves heat resistanceheat resistant, anti-light, resistant to hydrolysis
And antioxygenic property, and there is outstanding weatherability, glossiness and chemical resistance.Particularly trimethylolethane is occurring
Gu---when solid phase becomes, reversibly absorb and discharge substantial amounts of heat, and phase transition process has without being separated, degree of supercooling is light,
The features such as nontoxic, corrosion-free, No leakage, thus the phase-change heat-storage material that TME has technology and economic potential as a class is subject to
The extensive concern in the whole world.Recent domestic has carried out numerous studies to it, all obtain extensively should in thermal fiber and clothing
With, and having extended to medical treatment, health care, automobile, the field such as military, demand constantly increases, but due to the technology ridge of developed country
Disconnected, domestic technique falls behind and quality, content do not reach requirement so that it is develop the slowest.
The preparation method of trimethylolethane (TME) is divided into as neopentyl glycol (NPG), trimethylolpropane (TMP)
Discrimination method and hydrogenation method, neopentyl glycol (NPG), trimethylolpropane (TMP) discrimination method technique are the most ripe, trimethylolethane
(TME) what discrimination method produced now has two sets, by formaldehyde, propionic aldehyde under the conditions of highly basic (NaOH or Ca (OH) 2) property through condensation, steam
Send out, extraction, rectification form, and byproduct sodium formate or calcium formate, yield low consumption is high, and wastewater treatment capacity is big, and product quality meets not
The needs of downstream product processing.Domestic hydrogenation method produces only Jilin Chemical BASF and produces neopentyl glycol (NPG) device, domestic right
The research and development of neopentyl glycol, trimethylolpropane hydrogen addition technology are more, are hydrogenated with trimethylolethane currently without document report
Industrial problems research.
Summary of the invention
Technical solution of the present invention:
It is an object of the invention to provide a kind of method that continuous condensating hydrogenation method prepares trimethylolethane (TME), this
Kind of method can solve current calcium method, and to consume formaldehyde many, and flow process is complicated, and formates such as cannot process at the problem.
Technical solution of the present invention is as follows:
A kind of method that continuous condensating hydrogenation method prepares trimethylolethane, comprises the following steps:
1) under organic base catalytic effect, preparation 2,2-dihydroxymethyl propionic aldehyde condensation liquid it are condensed by formalin and propionic aldehyde；
1
2) by step 1) condensation liquid prepared removes unreacted excess formaldehyde and organic base and water through decompression distillation, obtains
Solid content is more than the 2 of more than 70%, 2-dihydroxymethyl propionic aldehyde concentrated solution；
3) by step 2) concentrated solution prepared carries out the first hydrogenation reaction in the first hydrogenation reactor and obtains hydrogen-rich liquid；
4) step 3) the hydrogen-rich liquid that obtains carries out the second hydrogenation reaction, the gas after being hydrogenated in the second hydrogenation reactor
Liquid mixed liquor；
5) described step 4) gas and liquid mixture that obtains enters after knockout tower separates and is refining to obtain three in distillating still
Hydroxymethyl ethane.
Preferably: described step 1) mol ratio of propionic aldehyde and formaldehyde is 1:1.5～7.5, described propionic aldehyde rubs with organic base
That ratio is 1:0.4-1.4, and described setting-up point is 30-60 DEG C.
It is further preferred that the mol ratio of formaldehyde and propionic aldehyde is 2.5, described propionic aldehyde is 0.6 with the mol ratio of alkali, described contracting
Closing reaction temperature and be 35-40 DEG C, reaction pressure is normal pressure.
Preferably, described step 1) organic base mixes with raw material formaldehyde and propionic aldehyde in the way of liquid, and medium is water or first
Alcohol, the preferred ammonia of described organic alkali catalyst, triethylamine or solid catalyst resin anion (R.A.), magnalium brucite.
Chromatography is done, it is to be understood that the main side reaction that condensation occurs is that discrimination directly occurs after being done by condensation liquid the most admittedly
Change the raw TME of reaction and formates.
Preferably, described step 2) decompression distillation pressure is-0.08～-0.076Mpa, temperature is 56-60 DEG C, pH8.5～
11, the response time is 8～12 hours.In scraper evaporator under negative pressure distillation rapidly remove unreacted formaldehyde, organic base and
Water, evaporation process obtains concentrated solution and evaporation condensate, makes the condensation liquid time of staying in vaporizer extremely short, in being possible to prevent
Between product 2, the decomposition of 2-dihydroxymethyl propionic aldehyde.Evaporation condensate can use as the stock media of condensation.Described step 2) 2,
In 2-dihydroxymethyl propionic aldehyde concentrated solution add 20% methanol or soft water after carry out step 3 again) operation.
It is further preferred that the structure of scraper evaporator (2), condensation liquid enters inside scraper evaporator from distributor,
Owing to distributor perforate is the direction stirred towards axle center from surrounding 360 °, condensation liquid is stirred after entering scraper evaporator immediately
On scraper plate get rid of and come to surrounding instantaneous dispersing, such internal structure can make condensation liquid enter the moment within scraper evaporator
Nebulize the vaporization of beneficially low-boiling point material of scattering to surrounding.The jacket structured Temperature Distribution that can make scraper evaporator is reasonable,
Low-boiling point material vaporization can be made rapidly to avoid again high boiling substance to lump in scraper evaporator.
Preferably, described step 3) the first catalyst for hydrogenation is nickel catalyst, catalyst diameter 2-8mm, highly
3-15mm, the first hydrogenation reaction pressure is 2-6MPa, temperature 60-110 DEG C, air speed 0.4-0.8m of liquid3/m3H, gas space
Speed 300-600Nm3/m3·h。
Preferably, described nickel catalyst manufacture method is:
1) deionized water being subsequently adding 5.6 times of weight during NaOH puts into beaker makes it fully dissolve, after being sufficiently stirred for
Sodium hydroxide solution is divided into two parts, half add the NaAlO of its 0.37% weight2And stirring fully makes it be completely dissolved
To material A, second half adds the SiO of 3.28 times of weight2And it is uniformly mixing to obtain material B, slowly drip after material B is stirred
Adding in material A, dropping limit, limit is stirred, and mixed solution transfer is put in the water-bath putting 40 DEG C in four-hole boiling flask after dropping completely
Constant temperature 24 hours, then place crystallization 48 hours at 100 DEG C, finally obtains solid phase be washed with deionized centrifugal for solidliquid mixture
Then it is placed at 100 DEG C to be dried and obtains carrier in 12 hours；
2) carrier and the co-precipitation of nickel nitrate: by 500ml25% nickel nitrate and the carrier first ultrasonic 30min that mixes, then constant temperature
Static two hours, then at 90 DEG C, stirring was evaporated until water cadre, then dried 12 hours at 100 DEG C, then roasting and molding,
Obtain material C；
3) the active component activating and reducing of catalyst, reduction temperature are 270～350 DEG C by material C hydrogen, adopt during activation
Nitrogen with 90% and the hydrogen of 10%, activation pressure 1.0～1.5MPa, complete nickel catalyst and make.
Gained catalyst is black cylinder, and carrier is SiO2And Al2O3, before activating and reducing, active component is that Ni is with NiO's
Form exists, and density of hydrogen too high catalyst reduction speed is the most broken.
Preferably, described step 4) the second catalyst for hydrogenation is copper chromium zinc aluminate catalyst, the second hydrogenation reaction pressure
For 2-6MPa, temperature 140-180 DEG C, air speed 0.1-0.25m of liquid3/m3·h。
Preferably, described copper chromium zinc aluminate catalyst manufacture method is:
1) a certain amount of 20wt%NaCO is first configured3Solution for standby, weighs copper nitrate 192g, zinc nitrate hexahydrate the most again
304g, ANN aluminium nitrate nonahydrate 489g, chromic nitrate 230g, add deionized water and be made into after 4000 milliliters of solution are sufficiently stirred for after mixing
To becoming nitrate solution；
2) add a small amount of sodium nitrate solution to flask, be heated to 80 DEG C-90 DEG C, then in flask, drip step 1) configuration
Nitrate solution, use 20wt%NaCO3Solution adjusts the pH to 9～10 in flask, is leached by precipitate, warp after reaction completely
Repeatedly with alkali metal ion in deionized water rinsing to flushing liquor less than 0.1wt%, then solid phase is dried 48 hours at 90 DEG C,
500 DEG C of roastings 24 hours, play sheet molding, obtain the hydrogenation catalyst of oxidation state, hydrogenating reduction, complete copper chromium zinc aluminate catalyst system
Make.
Preferably, described step 1) condensation reaction equipment uses continuous impact flow reactor, continuous for feedstock
Impact flow reactor is provided with charging aperture corresponding distributor, is provided with stirring paddle in described continuous impact flow reactor, described in stir
Mixing oar parallel with distributor height, described charging aperture, distributor and stirring paddle are respectively equipped with three, raw material formaldehyde and propionic aldehyde mixing
Liquid enters from the distributor of bottom, and soft water enters from intermediate distributor, and organic alkali catalyst enters from the top distributor.
Chuck within described continuous impact flow reactor is divided into upper and lower two-layer, and two-layer individually heats.
Preferably, described step 3) the first hydrogenation reactor employing gas-liquid-solid three-phase trickle bed hydrogenation reactor, fill new
Type nickel catalyst, it is therefore intended that 2,2-dihydroxymethyl propionic aldehyde are extremely unstable material, temperature is higher than 130 DEG C of easy decomposition,
Nickel series hydrogenating catalyst low temperature has higher activity, and gas-liquid-solid three-phase trickle bed hydrogenation reactor architectural characteristic can guarantee that nickel system
Catalyst is stable in Aquo System, and heat-sensitive materials is not easily decomposed.
It is further preferred that described titration bed hydroprocessing reactor is divided into two sections, between two sections, make upper and lower two equipped with a dividing plate
Section catalyst between at regular intervals, so have enough position catalyst fillings, avoid again material to tie in hydrogenation reactor
Block results in blockage.Titration bed hydroprocessing reactor jacket uses two sections of heating, needs to be warmed up to because material has just enter into hydrogenation reactor
Reach the temperature needed for reaction, and once start to react start highly exothermic, so the heat that upper end needs is more than lower end,
Temperature is separately controlled and is conducive to the control of whole reaction in order to avoid because of generation side reaction too high or too low for temperature, this reactor two sections
It is assembled with three thermometeies of upper, middle and lower, prepares to measure each section of temperature and be controlled by reaction temperature.
Preferably, described step 4) the second hydrogenation reactor employing bubble type Bed structure, it is connected on filling nickel system and urges
After the trickle bed low temperature hydrogenation reactor of agent, filling copper chromium aluminum zinc is the catalyst of key component, and corresponding raising is hydrogenated with temperature
Degree, it is ensured that the complete hydrogenolysis containing lipid by-product produced in condensation reaction, hydrogenation thoroughly, thus improves quality and the receipts of product
Rate.Fixed bed hydrogenation reactor charging is to enter, from top out from bottom distributor.So can effectively solve condensation reaction
The acetals of middle generation and the problem that hydro-conversion is trimethylolethane of lipid by-product, it is ensured that higher conversion and product
Quality.
It is further preferred that the distributor that bubbling bed hydrogenation reactor is is the bottom at reactor, allow reactant liquor and hydrogen
Gas enters distributor and goes out from top through intensive catalyst layer with reactant liquor hence into inside reactor, hydrogen from bottom
Coming, the outlet of two reactors has fine and closely woven screen cloth with the powder after preventing catalyst breakage along with entrained liquid sets to below
Standby.
Preferably, the main body of the distributor of described first hydrogenation reactor import is a hollow cylinder, cylinder
Upper bottom surface and bottom surface be provided with the hollow small cylinder of multiple protrusion, protrude one of small cylinder is uncovered,
Small cylinder is connected only one of which aperture with big cylinder, the diameter of small cylinder about 3～6mm, the diameter of aperture about 0.5mm,
The height of small cylinder about 1.5～3cm, is designed with beneficially material and enters full and uniform dispersion after hydrogenation reactor and come.
Preferably, described step 5) proportion 1.075～1.082 of distillating still Produced Liquid.
Preferably, the distributor perforate of scraper evaporator is the direction stirred towards axle center from surrounding 360 °, and condensation liquid enters
The scraper plate being stirred immediately after entering scraper evaporator gets rid of and comes to surrounding instantaneous dispersing, and such internal structure can make condensation liquid
Entering moment within scraper evaporator nebulizes the vaporization of beneficially low-boiling point material of scattering to surrounding.Jacket structured can making is scraped
The Temperature Distribution of plate vaporizer is reasonable, and low-boiling point material vaporization can be made rapidly to avoid again high boiling substance at scraper evaporator
Interior caking.
The technology of the present invention effect:
1, by-product is less, and quality is good, and flow process is shorter, and purification is relatively simple, the Novel ring of basic non-wastewater discharge
Protecting technique, equipment is few, and production cost is low, has stronger competitiveness, requires higher to hydrogenation plant and technology, is suitable for continuously
Large-scale production.
2, it is condensed the selection of stage alkaline catalyst, selects suitable base catalyst can effectively control condensation secondary anti-
The generation answered, every kind of base catalyst all can bring different impurity, and the complexity in evaporation stage remove impurity also will differ
Sample.
3, the distribution of condensation reaction charging, four kinds of raw material entrance condensation kettle positions and distributor type all can strong influences
The selectivity of raw material is had significant effect by the troubled water raw material.The raw material of condensation enters corresponding by respective entrance
Distributor, the stirring of condensation kettle is with three stirring paddles, and all correspondences are entering at three distributor height and positions, formaldehyde and propionic aldehyde
First passing through a blender before condensation kettle, formaldehyde and propionic aldehyde mix homogeneously are again from same point of condensation kettle bottom in a mixer
Cloth device enter condensation kettle, the height of this distributor is concordant with condensation kettle foot stirring paddle, distributor be diameter 5CM ring-type greatly
Little suitable with condensation kettle, soft water enters from intermediate distributor as medium, and triethylamine enters condensation kettle from upper distributor.Three points
The position formaldehyde propionic aldehyde blender of cloth device has 20CM to bottom, has 50CM to soft water distributor, and soft water has to triethylamine distributor
50CM。
3, the structure of condensation kettle, internal structure affects the mixability of raw material, jacket structured affects inside condensation kettle
Temperature, thus affect condensation raw material selectivity.The chuck of condensation kettle is divided into upper and lower two-layer, and two-layer individually heats, because of bottom
Reaction is somewhat violent, and this reaction is exothermic reaction, so temperature of lower may be the most higher, for convenience of regulation temperature so taking
Two sections are heated respectively,
4, the structure of scraper evaporator, condensation liquid enters inside scraper evaporator from distributor, due to distributor perforate
Being the direction stirred towards axle center from surrounding 360 °, the scraper plate that condensation liquid is stirred after entering scraper evaporator immediately gets rid of to four
Week, instantaneous dispersing came, and such internal structure can make condensation liquid entrance moment within scraper evaporator nebulize scattered to surrounding
Have the vaporization of beneficially low-boiling point material.The jacket structured Temperature Distribution that can make scraper evaporator is reasonable, can make low rapidly
Boilers vaporization avoids again high boiling substance to lump in scraper evaporator.
5, in evaporation and concentration liquid, add methanol or the soft water of 20%.And stirring is sufficiently mixed and is beneficially hydrogenated with.
6, the design of the distributor of the first hydrogenation reactor import, distributor main body is a hollow cylinder, cylinder
Inlaying a lot of prominent small cylinders on the upper bottom surface of body and bottom surface, protrude one of small cylinder is complete uncovered
, small cylinder and an only one of which aperture of great circle cylinders contact, beneficially material are the most equal after entering hydrogenation reactor
Even spread out.
7, the structure of hydrogenation reactor, titration bed hydroprocessing reactor is divided into two sections, makes up and down equipped with a dividing plate between two sections
Between two-stage catalytic agent at regular intervals, so have enough position catalyst fillings, avoid again material in hydrogenation reactor
Caking results in blockage.Titration bed hydroprocessing reactor jacket uses two sections of heating, needs to heat up because material has just enter into hydrogenation reactor
Arrive reaction needed for temperature, and once start to react start highly exothermic, so upper end need heat be more than under
End, is separately controlled temperature and is conducive to the control of whole reaction in order to avoid because of generation side reaction too high or too low for temperature, this reactor
Two sections are assembled with three thermometeies of upper, middle and lower, prepare to measure each section of temperature and are controlled by reaction temperature, and bubbling bed hydrogenation is anti-
The distributor answering device to be is the bottom at reactor, allows reactant liquor and hydrogen enter distributor from bottom hence in reactor
Portion, with reactant liquor through intensive catalyst layer from top out, the outlet of two reactors has fine and closely woven screen cloth to hydrogen
To prevent the powder after catalyst breakage along with entrained liquid is to equipment below.
8, the shape of catalyst selects, and the shapes and sizes of catalyst select difference, decides hydrogen, material and activity group
Divide and directly can be fully contacted, if the shapes and sizes of catalyst select appropriately to turn avoid with material hydrogenation to urge the most simultaneously
The situation that agent crushes at high temperature under high pressure.
When 9, using distillating still distillation extraction crystal solution, must strictly controlling of the proportion of crystal solution, otherwise on crystallization rank
Section will not occur without the situation that crystal separates out.Drying stage must use special drying device, because of TME dissolubility in water
Very big, the TME being centrifuged out also has the moisture of about 1%, is dried according to general exsiccator, will cause at temperature-rise period
TME melts, so product is easy to melt when dry, causes waste.The present invention uses the rotary kiln can be effective
The problem solving to cause product to melt because moisture is too high.
10, using the inventive method ultimate yield can reach more than 75%, product purity reaches more than 99.5%.
Accompanying drawing explanation
Fig. 1: trimethylolethane gas chromatogram；
Condensation catalyst concentrated solution gas chromatogram figure made by Fig. 2: embodiment 1 triethylamine；
Fig. 3: embodiment 2 ammonia makees condensation catalyst concentrated solution gas chromatogram figure；
Fig. 4: embodiment 3 magnalium neatly masonry condensation catalyst concentrated solution gas chromatogram figure；
Fig. 5: schematic flow sheet of the present invention；
Distributor schematic flow sheet in Fig. 6: the present invention the first hydrogenation reactor；
Distributor schematic flow sheet in Fig. 7: the present invention the first hydrogenation reactor；
Wherein: impact flow reactor 1 continuously, charging aperture 1-1, distributor 1-2, stirring paddle 1-3, scraper evaporator 2, evaporation
Condenser 3, the first hydrogenation reactor 4, the second hydrogenation reactor 5, gas-liquid separator 6, cylinder 6, small cylinder 7, hole 8.
Detailed description of the invention
Further illustrate the present invention below in conjunction with embodiment, but the scope of protection of present invention is not limited to implement
The scope of example statement.
Analytical conditions for gas chromatography
Analytical tool: welfare gas chromatograph (GC-9790plus) chromatographic column: MEGA-1701/30m*0.32mm*
0.45um。
Gas phase analysis method: area normalization method.
Gas phase analysis condition: initial temperature 150 DEG C keeps 1min,
10 DEG C/min of heating rate, final temperature 250 DEG C, keep 8min, injector temperature 300 DEG C, detector temperature 300 DEG C.
Column temperature is temperature programming.
Embodiment 1
A kind of method that continuous condensating hydrogenation method prepares trimethylolethane, comprises the following steps:
1) in percussion flow microcosmic hybrid reactor, add the water of 2/3 volume of total measurement (volume) or reclaim dilute formalin,
In the following proportions；Formaldehyde, propionic aldehyde, triethylamine and the soft water ratio with mol ratio as 2.5:1:0.6:20 adds condensation kettle, condensation
Still temperature controls to produce fluctuation because there is side reaction at the pH of 30-40 DEG C of condensation liquid, and the pH in condensation kettle controls 8.5
Be 8～12 hours to the 8.9. time of staying, obtain containing 8%-18%2,2-dihydroxymethyl propionic aldehyde, 1.5%-3% the most anti-
The formaldehyde answered, the alkali of 0.5%-1.5%, single bisacetal class of 1%-3% and lipoid substance, the water of 75%-85%；
2) by step 1) condensation liquid prepared removes unreacted excess formaldehyde and organic base and water through decompression distillation, obtains
Containing 50%-70% 2,2-dihydroxymethyl propionic aldehyde, the acetal of trimethylolethane and lipid concentrated solution；Reduction vaporization passes through scraper plate
Vaporizer can preferably remove unreacted formaldehyde and organic base, and the pressure of evaporation process is-0.076mpa to-0.08mpa, temperature
Degree is for obtaining concentrated solution after 50-60 DEG C of distillation；
Evaporation condensate reclaims and can use as the medium soft water required for condensation course,
3) by step 2) concentrated solution prepared carries out the first hydrogenation reaction in the first hydrogenation reactor and obtains hydrogen-rich liquid, and
One hydrogenation reaction pressure is 2-6MPa, temperature 60-110 DEG C, air speed 0.4-0.8m of liquid3/m3H, gas space velocity 300-
600Nm3/m3H, the crude carbinol adding 20% in concentrated solution is conducive to 2, the hydrogenation of 2-dihydroxymethyl propionic aldehyde；
4) step 3) the hydrogen-rich liquid that obtains carries out the second hydrogenation reaction, the gas after being hydrogenated in the second hydrogenation reactor
Liquid mixed liquor；Described step 4) the second catalyst for hydrogenation is 250-325 mesh copper chromium zinc aluminate catalyst, the second hydrogenation reaction pressure
Power is 2-6MPa, temperature 140-180 DEG C, air speed 0.1-0.25m of liquid3/m3·h；
5) described step 4) gas and liquid mixture that obtains enters the gas-liquid separation of knockout tower elder generation and then carries out essence in rectifying still
Prepare trimethylolethane.
Described step 5) high-pressure gas-liquid separates after the cooled cooling of gas and liquid mixture, and gas is that the hydrogen circulation of excess makes
With, liquid enters in compression rectification tower after decompression, tower top pressure 0.2MPa, column bottom temperature 120-140 DEG C, tower top partial reflux
Control top temperature 90-105 DEG C；Bottom distillating still, sample analysis proportion proportion more than 100 DEG C reaches to start to adopt when more than 1.075
Go out to crystallizer crystallisation by cooling, centrifugal, dry, packaging, in Recycling Mother Solution to rectifying column.The detection of finished product result is shown in Table 1, three hydroxyls
Methyl ethane finished product gas chromatogram is shown in that Fig. 1, triethylamine make condensation catalyst step 2) concentrated solution gas chromatogram is shown in Fig. 2.
Table 1 trimethylolethane finished product detection result
Embodiment 2
A kind of method that continuous condensating hydrogenation method prepares trimethylolethane, comprises the following steps:
1) in percussion flow microcosmic hybrid reactor, add the water of 2/3 volume of total measurement (volume) or reclaim dilute formalin work
For bottom water, in the following proportions；Formaldehyde, propionic aldehyde, ammonia and the soft water ratio with mol ratio as 2.5:1:0.6:20 adds condensation kettle,
Condensation kettle temperature controls at 30-40 DEG C, and the pH of condensation liquid can produce fluctuation because there is side reaction, and the pH in condensation kettle controls
It is 8～12 hours in 8.5 to 11 time of staying, obtains condensation liquid；
2) by step 1) condensation liquid prepared uses embodiment 1 condition to carry out decompression distillation, and the concentrated solution obtained is containing a large amount of
White solid, analyzing this white solid through gas chromatogram (Fig. 3) is hexamethylenamine.When ammonia makees base catalyst formaldehyde and
Ammonia reaction generates hexamethylenamine.Simultaneously ammonia when evaporation process is difficult to remove easy after catalyst poisoning, therefore ammonia
Do the liquid base being condensed also to need to optimize further.
Embodiment 3
Add 300ml soft water in four-hole boiling flask, add 8g magnalium neatly masonry condensation catalyst, leak at pyriform separatory
Bucket is respectively charged into 230ml formaldehyde (37%), the propionic aldehyde (99.5%) of 90ml.Allow stirring that catalyst is well dispersed in soft water it
After start to be slowly added dropwise formaldehyde and propionic aldehyde, flask is placed in thermostat water bath, makes temperature in flask be maintained at about 35 DEG C.Three arrive
Within six hours, drip propionic aldehyde and formaldehyde, drip and continue stirring afterwards, little to stopping amounting to 10 from starting to drip propionic aldehyde and formaldehyde
Time.Chatting reactant liquor on by be placed in rotary evaporator and obtain concentrated solution after negative pressure evaporation and do chromatography, result is shown in Fig. 4.By Fig. 4
Understand....Brucite is doing the excellent catalytic effect being condensed, and makes formaldehyde and propionic aldehyde be largely converted into 2,2-dihydroxymethyl propionic aldehyde,
From the point of view of on surface, brucite can be as condensation base catalysis.But in follow-up experiment, claim 10g brucite to be dissolved in 300ml and steam
Distilled water, filters out brucite after stirring, by chat the aqueous solution obtained and put in beaker and heat water on electric furnace
Divide and be evaporated, finally obtain 0.52g whiteness.So brucite can ionize out salt in water, its content is 0.52/10=
5.2%.This content is the biggest for product, and desalination is a complicated process, contracts so brucite does
The base catalyst closed also needs to optimize further.
Embodiment 4
Take 1000ml hydrogenation reaction reactant liquor out in beaker, distill and survey the proportion at its 100 DEG C, and after cooling down
Survey its solid content.Experimental result such as table 2 below.
Table 2 reactant liquor distills in beaker and surveys the proportion at its 100 DEG C
| Sample | Temperature | Proportion | Solid-to-liquid ratio |
| 1 | 100℃ | 1.057 | 5% |
| 2 | 100℃ | 1.065 | 10% |
| 3 | 100℃ | 1.071 | 36% |
| 4 | 100℃ | 1.075 | 60% |
| 5 | 100℃ | 1.082 | 62% |
As shown in Table 2: the proportion at distillating still distillation stage Produced Liquid must strictly control otherwise to cause mother solution to follow in a large number
Ring increases the load of distillating still, results even in mother solution retention effects and normally produces, and controlling Produced Liquid proportion well can be great
Increase product yield and steam saving energy consumption.The proportion 1.075～1.082 of the Produced Liquid that the application is suitable.
Embodiment 5
Concentrated solution before hydrogenation adds soft water and methanol and independent concentrated solution is made comparisons, measure the product after hydrogenation
The residual aldehyde of thing.
The residual aldehyde of the product after table 3 hydrogenation
As shown in Table 3: if concentrated solution is added without soft water or methanol dilution and is susceptible to density of hydrogen declines when
Be hydrogenated with incomplete situation, if additionally actual production process reach a conclusion not in concentrated solution add soft water or methanol titration bed
Hydrogenation reactor results in blockage.So adding entering smoothly of a certain amount of methanol of about about 20% or soft water beneficially hydrogenation reaction
OK.
Embodiment 6
Low temperature hydrogenation, second segment bubble type fluid bed reactor is taked at hydrotreating stage first paragraph titration bed hydroprocessing reactor
Take heat up hydrogenation, when two hydrogenation reactors all take 60 DEG C of-110 DEG C of yields of low temperature hydrogenation than second segment be warmed up to 140 DEG C-
The yield of 180 DEG C of products will low 3%-9%.
Embodiment 7
Catalyst obtained above is made difformity and size, after activating and reducing, tests its hydrogenating reduction respectively
Ability is shown in Table 4.
The impact on hydrogenating reduction ability of table 4 catalyst size
| Shape | 120 DEG C, 5.5MPA, residual aldehyde | Remarks |
| Powder | 0% | Catalyst attrition is fast |
| Lamellar | 0% | Under high pressure broken |
| Cylinder 2*5 | 0% | Resistance to pressure is general |
| Cylinder 2*8 | 0% | |
| Cylinder 3*5 | 0% | |
| Cylinder 3*8 | 0% | |
| Cylinder 5*10 | 0.001 | Contact area reduces |
But be conducive to material and catalyst as shown in Table 4 when catalyst makes powder and lamellar contacts powder catalytic
Agent can penetrate screen cloth along with material, makes in material containing impurity, also makes catalyst loss reduce the service life of catalyst, cylinder
Start that the incomplete phenomenon of hydrogenation occurs when body catalyst is at diameter with highly for 5*10mm, and cylinder more small catalyst more holds
Easily wearing and tearing in hydrogenation reactor, so the preferred cylinder diameter of catalyst and height are 2～4*5～10mm, optimum is 3*
8mm,.
Embodiment 8
Using preferred catalyst to carry out Hydrogenation Experiment at different temperatures, the impact of aldehyde residual on hydrogenation liquid is shown in Table 5.
The impact on hydrogenating reduction ability of table 5 catalyst size
Temperature hydrogenation reaction between 120 DEG C-140 DEG C is very complete as shown in Table 5, too high or too low for temperature all makes hydrogenation anti-
Should be incomplete.
Can be seen that the base catalyst in the stage of being condensed chooses triethylamine the most properly by above enforcement, magnalium neatly
Stone and anion exchange resin are treated to study further, and the yield affecting whole end product was mainly in the condensation stage, because contracting
Conjunction stage condensation raw material formaldehyde, propionic aldehyde are the aldehyde that two kinds of chemisms are the strongest, multiple reaction can occur under certain condition, produce
Different materials, so both reactions are sufficiently complex chemical reactions.Not only can generate target product 2,2-dihydroxy first
Base propionic aldehyde, also can produce other by-product, first formaldehyde and understand self party, but polymerization is how many in reversible reaction condensation liquid
Can there is a small amount of polymer, formaldehyde also can occur cannizzaro's reaction to generate trihydroxy methyl in the basic conditions with intermediate product
Ethane and formates, simultaneously 2,2-dihydroxymethyl propionic aldehyde is also an aldehydes not having@H, and self also can be condensed into trimer.?
In the primary response of condensation, a part formaldehyde and a part propionic aldehyde are under the effect of alkali, and a part formaldehyde and a part propionic aldehyde contract
Symphysis becomes@-methylol propionic aldehyde, and this reaction intermediate and instability thereof the most somewhat heat Variational Solution Used and cause not
Can continue and propionic aldehyde is condensed generation 2,2-dihydroxymethyl propionic aldehyde.So the selection of catalyst and the temperature of reaction, pH control all
The time of staying is all and important, the fewest by controlling the side reaction that condensation course makes condensation reaction produce, can be very big
The productivity of raising end product TME.Ultimate yield can reach more than 75%, and product purity reaches more than 99.5%.
Embodiment 9
Use embodiment 1 method, wherein, as described in Figure 5:
Described step 1) the condensation reaction equipment continuous impact flow reactor 1 of employing, for the continuous percussion flow of feedstock
Reactor is provided with charging aperture 1-1 corresponding distributor 1-2, is provided with stirring paddle 1-3 in described continuous impact flow reactor, described
Stirring paddle 1-3 is the most parallel with distributor 1-2, and described charging aperture 1-1, distributor 1-2 and stirring paddle 1-3 are respectively equipped with three,
Raw material formaldehyde and propionic aldehyde mixed liquor enter from the distributor of bottom, and soft water enters from intermediate distributor, organic alkali catalyst from
The top distributor enters.
Chuck within described continuous impact flow reactor 1 is divided into upper and lower two-layer, and two-layer individually heats.
Described step 3) the first hydrogenation reactor employing gas-liquid-solid three-phase trickle bed hydrogenation reactor 4；Described step 4) the
Two hydrogenation reactors use bubble type Bed.
The main body of the distributor of described first hydrogenation reactor import is a hollow cylinder 6, the cylindrical upper end
Face and bottom surface are provided with the hollow small cylinder 7 of multiple protrusion, and protrude one of small cylinder 7 is uncovered, roundlet
Cylinder is connected only one of which hole 8 with big cylinder, the diameter of small cylinder 7 about 3～6mm, and the diameter 0.3～0.6mm in hole 8 is little
The height 1.5～3cm of cylinder 7, is designed with beneficially material and enters full and uniform dispersion after hydrogenation reactor and come, see Fig. 6,7.
The above embodiments are only the preferred technical solution of the present invention, and are not construed as the restriction for the present invention, this Shen
Embodiment in please and the feature in embodiment, can mutual combination in any in the case of not conflicting.The protection model of the present invention
Enclose the technical scheme should recorded with claim, including the equivalent side of technical characteristic in the technical scheme that claim is recorded
Case is protection domain.Equivalent the most in this range is improved, also within protection scope of the present invention.
Claims (10)
1. the method that a continuous condensating hydrogenation method prepares trimethylolethane, it is characterised in that comprise the following steps:
1) under organic base catalytic effect, preparation 2,2-dihydroxymethyl propionic aldehyde condensation liquid it are condensed by formalin and propionic aldehyde；
2) condensation liquid prepared by step 1) removes unreacted excess formaldehyde, organic base and water through decompression distillation, obtains 2,2-
Dihydroxymethyl propionic aldehyde concentrated solution；
3) by step 2) concentrated solution prepared carries out the first hydrogenation reaction in the first hydrogenation reactor and obtains hydrogen-rich liquid；
4) the hydrogen-rich liquid that step 3) obtains carries out the second hydrogenation reaction in the second hydrogenation reactor, and the vapour-liquid after being hydrogenated is mixed
Close liquid；
5) the vapour-liquid mixed liquor that described step 4) obtains enters after knockout tower carries out gas-liquid separation and is refining to obtain three hydroxyls at distillating still
Methyl ethane.
Method the most according to claim 1, it is characterised in that: the mol ratio of described step 1) propionic aldehyde and formaldehyde be 1:1.5 ~
7.5, described propionic aldehyde is 1:0.4-1.4 with the mol ratio of organic base, and described setting-up point is 30-60 DEG C, pH 8.5 ~ 11,
Response time is 8 ~ 12 hours.
Method the most according to claim 1, it is characterised in that: described step 1) organic base in the way of liquid with raw material formaldehyde
Mixing with propionic aldehyde, medium is water or methanol, and described organic alkali catalyst is triethylamine or resin anion (R.A.) or magnalium brucite.
Method the most according to claim 1, it is characterised in that: described step 2) decompression distillation pressure is-0.08 ~-
0.076Mpa, temperature is 56-60 DEG C, described step 2) 2,2-dihydroxymethyl propionic aldehyde concentrated solution adds methanol or the soft water of 20%
After carry out step 3) operation again.
Method the most according to claim 1, it is characterised in that: described step 3) the first hydrogenation reaction be catalyst be that nickel system urges
Agent, catalyst diameter 2 ~ 4 mm, highly 5 ~ 10mm；
First hydrogenation reaction pressure is 2-6MPa, temperature 60-110 DEG C, air speed 0.4-0.8m of liquid3/m3H, gas space velocity
300-600 Nm3/m3▪h。
Method the most according to claim 1, it is characterised in that: described step 4) the second catalyst for hydrogenation is copper chromium aluminum zinc
Catalyst, the second hydrogenation reaction pressure is 2-6MPa, temperature 140-180 DEG C, air speed 0.1-0.25m of liquid3/m3▪h。
Method the most according to claim 1, it is characterised in that: described step 1) condensation reaction equipment uses continuous percussion flow anti-
Answering device (1), the continuous impact flow reactor for feedstock is provided with charging aperture (1-1) corresponding distributor (1-2), described company
Being provided with stirring paddle (1-3) in continuous impact flow reactor, described stirring paddle (1-3) is the most parallel with distributor (1-2), described in enter
Material mouth (1-1), distributor (1-2) and stirring paddle (1-3) are respectively equipped with three, and raw material formaldehyde and propionic aldehyde mixed liquor are from bottom
Distributor enters, and soft water enters from intermediate distributor, and organic alkali catalyst enters from the top distributor；
The chuck that described continuous impact flow reactor (1) is internal is divided into upper and lower two-layer, and two-layer individually heats.
Method the most according to claim 1, it is characterised in that: described step 3) the first hydrogenation reactor uses gas-liquid-solid three-phase
Trickle bed hydrogenation reactor (4)；Described step 4) the second hydrogenation reactor uses bubble type Bed.
Method the most according to claim 8, it is characterised in that: the main body of the distributor of described first hydrogenation reactor is one
Hollow cylinder (6), cylindrical upper bottom surface and bottom surface are provided with the hollow small cylinder (7) of multiple protrusion, roundlet
Protrude one of cylinder (7) is uncovered, and small cylinder is connected only one of which hole (8) with big cylinder, small cylinder (7)
Diameter about 3 ~ 6 mm, the diameter 0.3 ~ 0.6mm of hole (8), the height 1.5 ~ 3cm of small cylinder (7).
Method the most according to claim 1, it is characterised in that: the proportion of described step 5) distillating still Produced Liquid 1.075 ~
1.082。
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108997082A (en) * | 2018-09-10 | 2018-12-14 | 武汉中能恒信工程技术有限公司 | A method of catalysis trimethylolpropane condensation reaction |
| CN114349595A (en) * | 2022-01-07 | 2022-04-15 | 万华化学集团股份有限公司 | Method for recycling by-product of BDO (methanol to ethane) prepared by allyl alcohol method |
| CN115286484A (en) * | 2022-09-05 | 2022-11-04 | 安徽普利优新材料有限公司 | Production process and preparation method of trimethylolethane |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102391070A (en) * | 2011-10-19 | 2012-03-28 | 上海华谊（集团）公司 | Method for producing trimethylolpropane by utilizing formaldehyde |
| 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 |
| CN105669370A (en) * | 2016-03-04 | 2016-06-15 | 江苏清泉化学股份有限公司 | Preparation method of trimethylolethane |
-
2016
- 2016-08-20 CN CN201610696961.XA patent/CN106278817A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102391070A (en) * | 2011-10-19 | 2012-03-28 | 上海华谊（集团）公司 | Method for producing trimethylolpropane by utilizing formaldehyde |
| 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 |
| CN105669370A (en) * | 2016-03-04 | 2016-06-15 | 江苏清泉化学股份有限公司 | Preparation method of trimethylolethane |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108997082A (en) * | 2018-09-10 | 2018-12-14 | 武汉中能恒信工程技术有限公司 | A method of catalysis trimethylolpropane condensation reaction |
| CN108997082B (en) * | 2018-09-10 | 2021-12-24 | 武汉中能恒信工程技术有限公司 | Method for catalyzing trimethylolpropane condensation reaction |
| CN114349595A (en) * | 2022-01-07 | 2022-04-15 | 万华化学集团股份有限公司 | Method for recycling by-product of BDO (methanol to ethane) prepared by allyl alcohol method |
| CN114349595B (en) * | 2022-01-07 | 2023-12-19 | 万华化学集团股份有限公司 | Method for recycling BDO byproducts of allyl alcohol method |
| CN115286484A (en) * | 2022-09-05 | 2022-11-04 | 安徽普利优新材料有限公司 | Production process and preparation method of trimethylolethane |
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