CN105175228B - A kind of calcium method neopentyl glycol preparation process - Google Patents
A kind of calcium method neopentyl glycol preparation process Download PDFInfo
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- CN105175228B CN105175228B CN201510549661.4A CN201510549661A CN105175228B CN 105175228 B CN105175228 B CN 105175228B CN 201510549661 A CN201510549661 A CN 201510549661A CN 105175228 B CN105175228 B CN 105175228B
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- neopentyl glycol
- formaldehyde
- calcium
- isobutylaldehyde
- calcium hydroxide
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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
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/94—Use of additives, e.g. for stabilisation
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention relates to a kind of using calcium hydroxide as the production technology of catalyst preparation neopentyl glycol.A kind of calcium method neopentyl glycol preparation process uses isobutylaldehyde, formaldehyde as raw material, using calcium hydroxide as catalyst, by being condensed, evaporate, distillation process, prepares neopentyl glycol, and in the condensation process, isobutylaldehyde, formaldehyde kilogram volume ratio that feeds intake are 1:1.5‑2.0；Molar ratio is isobutylaldehyde:Formaldehyde:Calcium hydroxide=1:2.5‑3.5:0.58‑0.65；The material concentration is that isobutylaldehyde is 20 25%, and concentration of formaldehyde is 12 15%, and calcium hydroxide is 8 10%.Preparation process of the present invention is fed intake using the catalyst program of innovation, is expanded formaldehyde and is fed intake molecular proportion, can significantly improve the conversion ratio of neopentyl glycol, neopentyl glycol conversion ratio be made to reach more than 94%, 98 grades of products of major product neopentyl glycol reach 70%.
Description
Technical field
It is new by catalyst preparation of calcium hydroxide more particularly, to one kind the present invention relates to a kind of neopentyl glycol preparation process
The production technology of pentanediol.
Background technology
Neopentyl glycol is widely used, mainly for the manufacture of polyester resin, polyurethane resin, synthetic lubricant fluid, plasticizer etc.,
Its derivative is mainly used in automobile, weaving, medicine, coating, plastics and oil product.With social development and the level of consumption
It improves, social demand is increasing, but China's technical merit lags, and constrains the development of neopentyl glycol industry.
Before there are mainly two types of common neopentyl glycol preparation methods, one kind is that Alder that occurs under organic base catalytic
Back end hydrogenation is reacted, product quality is relatively preferable, but cost is higher, does not have byproduct formates, constrains large-scale development；It is another
Kind is that Toulon occurs for catalyst using sodium hydroxide to react, advantage of lower cost, but how new penta easily occurs under basic conditions
The side reactions such as glycol cause product quality low.
To solve foregoing problems, Chinese invention patent application《A kind of method that calcium method prepares neopentyl glycol》（Patent application
Number：CN 201210218004.8）It proposes using the production method that calcium hydroxide is catalyst preparation neopentyl glycol, using this
Technique, raw material calcium hydroxide is lower than sodium hydroxide price, and the added value of byproduct formic acid calcium is high；The hydroxyl value of neopentyl glycol product
Height, it is high-quality.But impurity and raising byproduct formic acid are brought into regard to how improving neopentyl glycol conversion ratio, removing calcium hydroxide in text
Calcareous amount etc. is not discussed, therefore the neopentyl glycol and first of high quality can not be prepared according to method disclosed in the application for a patent for invention
Sour calcium.
Invention content
The present invention is in view of the shortcomings of the prior art, propose a kind of new for catalyst preparation neopentyl glycol using calcium hydroxide
Technique.Using this technique, it is possible to reduce the generation of side reaction, improve major product hydroxyl value, it is high-quality, can reduce catalyst into
This, improves byproduct added value.
The technical solution adopted in the present invention：
A kind of calcium method neopentyl glycol preparation process uses isobutylaldehyde, formaldehyde as raw material, using calcium hydroxide as catalyst, leads to
Condensation, evaporation, distillation process are crossed, prepares neopentyl glycol, in the condensation process, isobutylaldehyde, formaldehyde kilogram volume ratio that feeds intake are
1:1.5-2.0；Molar ratio is isobutylaldehyde:Formaldehyde:Calcium hydroxide=1:2.5-3.5:0.58-0.65；The material concentration is
Isobutylaldehyde is 20-25%, concentration of formaldehyde 12-15%, calcium hydroxide 8-10%.
The calcium method neopentyl glycol preparation process, condensation process use following feeding mode：Formaldehyde is disposably put into,
Isobutylaldehyde at the uniform velocity adds in, and calcium hydroxide program adds in, i.e., first half term adds in the 1/4 of total amount, and the second half adds in the 3/4 of total amount；Contracting
Reaction temperature control is closed at 35-55 DEG C, the reaction time is 3-5 hours.
Beneficial effects of the present invention：
1st, calcium method neopentyl glycol preparation process of the present invention, is fed intake using the catalyst program of innovation, is expanded formaldehyde and is fed intake point
Sub- ratio can significantly improve the conversion ratio of neopentyl glycol, neopentyl glycol conversion ratio be made to reach more than 94%, major product neopentyl glycol
98 grades of products reach 70%.
2nd, calcium method neopentyl glycol preparation process of the present invention, passes through bridging agent, the addition of sulfide precipitation agent, it is possible to reduce secondary
The generation of reaction improves byproduct calcium formate purity and reaches more than 99%.It is changed, improved by the transformation of catalyst and byproduct
Byproduct added value, reduces catalyst cost, and condensation cost can decline 1000 yuan or more.
3rd, calcium method neopentyl glycol preparation process of the present invention, small investment, quick, simple for process, easy to operate, main product quality
It measures, byproduct added value height.By the recycling of dilute formaldehyde, unit product can reduce formaldehyde and consume 180 kilograms, isobutylaldehyde consumption
30 kilograms of reduction, it is easy to utilize.
4th, calcium method neopentyl glycol preparation process of the present invention, can reduce catalyst cost, hence it is evident that reduce the generation of side reaction.It carries
High major product hydroxyl value, it is high-quality.
Specific embodiment
Neopentyl glycol new preparation process of the present invention is using isobutylaldehyde, formaldehyde as raw material, using calcium hydroxide as catalyst and instead
Object is answered, neopentyl glycol is prepared by condensation；After reaction, with first acid for adjusting pH value, bridging agent and sulfide precipitation agent are added in,
Under weak basic condition, make silicon, magnesium, aluminium and a small amount of beavy metal impurity precipitation, then remove impurity by filter plant；It adjusts again
PH value is saved, formaldehyde excessive in condensation liquid is removed by pressurizing tower, full gear liquid enters evaporator, and dilute formaldehyde returns to condensation dispensing；
Neopentyl glycol and water rise to evaporating column in the form of steam state in evaporation process, after overhead condensation water spray, due to the two boiling point not
Together, neopentyl glycol is reentered in evaporating column, and the condensed device of water removes evaporating column, and so as to achieve the effect that concentration, calcium formate is brilliant
Body eluriates leg through proprietary technology after being precipitated and is put into crystallization crystallization in motion device, so as to obtain high-quality byproduct calcium formate；Liquid is evaporated through steaming
It evaporates tower further to concentrate, is most sliced into neopentyl glycol finished product through cooling afterwards.
Below by specific embodiment, technical scheme of the present invention is described in further detail.
Embodiment 1
The present embodiment calcium method neopentyl glycol preparation process, uses isobutylaldehyde, formaldehyde as raw material, using calcium hydroxide as catalysis
Agent, unlike the prior art：In condensation process, isobutylaldehyde, formaldehyde feed intake kilogram volume ratio as 1:1.5-2.0；It feeds intake
Molar ratio is isobutylaldehyde:Formaldehyde:Calcium hydroxide=1:2.5-3.5:0.58-0.65；The material concentration is that isobutylaldehyde is 20-
25%, concentration of formaldehyde 12-15%, calcium hydroxide 8-10%.
Material concentration is that isobutylaldehyde is 20-25%, concentration of formaldehyde 12-15%, calcium hydroxide 8-10%.
Preceding percentage concentration refers to weight percent in engineering.Kilogram volume ratio is polyalcohol industry category language, i.e. kilomol
Volume ratio refers to generating 1 kilomol neopentyl glycol in 1 cubic metre of solution.
Neopentyl glycol preparation process of the present invention expands formaldehyde and feeds intake molecular proportion, can improve the conversion ratio of neopentyl glycol, carry
High neopentyl glycol conversion ratio is more than 94%, and for high conversion rate in current colleague 4%, 98 grades of products of major product neopentyl glycol reach 70%.
It can obviously reduce the generation of side reaction.
Embodiment 2
Neopentyl glycol preparation process described in the present embodiment, the difference lies in be condensed the reaction of process with embodiment 1
At 35-55 DEG C, the reaction time is 3-5 hours for temperature control；In view of the condensation reaction of neopentyl glycol（In two steps）, first
Ground beetle aldehyde occurs Alder that with a hydrogen on isobutylaldehyde and reacts, and does not consume alkali, but necessarily react under alkaline condition, second step
Disproportionated reaction occurs for aldehyde, and oxidation of formaldehyde is formic acid, consumes alkali, maintains alkaline environment, methylol isobutylaldehyde is reduced to alcohol, therefore adopts
With following feeding mode：It is disposably put into for formaldehyde, isobutylaldehyde at the uniform velocity adds in, and calcium hydroxide program adds in, i.e., first half term adds
Enter the 1/4 of total amount, the second half adds in the 3/4 of total amount.
Embodiment 3
The calcium method neopentyl glycol preparation process of the present embodiment, as different from Example 2：It is condensed the molar ratio of process
For isobutylaldehyde：Formaldehyde：Calcium hydroxide=1:3.0:0.6, the volume ratio that feeds intake is 1:1.8, calcium hydroxide uses purity as 92-95%'s
Calcareous white lime, feeds intake for 3-10 minutes in advance and program is put into, and the 1/4 of first half term otal investment, the 3/ of the second half otal investment
4, and finished simultaneously with isobutylaldehyde.
Embodiment 4
Neopentyl glycol preparation process described in the present embodiment, the difference lies in further with foregoing embodiments：
It is 7-8 that pH value is adjusted after condensation, and the sulfide precipitation agent is Ca2S, dosage are the 10-20PPm of liquor capacity, are utilized
Principle is precipitated, the heavy metal for being slightly soluble in water is made to form extremely difficult molten sulfide；The bridging agent is formaldehyde and dicyandiamide polycondensation, is used
Ammonium chloride is as catalyst and modifying agent, molar ratio 2.3:1:0.63, the cation superpolymer with quaternary amine base of generation,
Using the hydrogen bond equimolecular intermolecular forces of quaternary amine base, the Mg (OH) with being insoluble in water in condensation liquid2、Na2SiO3、Al(OH)3And its
He builds bridge at heavy metal sulfide, forms larger floc sedimentation, and convenient for settling and filtering, dosage is the 3-6PPm of liquor capacity；Institute
The calcium formate crystallization crystallization in motion device stated is complete set of equipments, using calcium formate and the different solubility of neopentyl glycol, is accelerated by gravity
Degree, classification increases calcium formate crystalline substance paddle ratio, so as to obtain the byproduct of high-quality.
Embodiment 5
Neopentyl glycol preparation process described in the present embodiment, the difference lies according to traditional mode of production work with embodiment 4
Skill can prepare high-quality neopentyl glycol through distilling, being sliced.
Embodiment 6
The neopentyl glycol preparation process of the present embodiment, with foregoing embodiments the difference lies in：It is removed using following
General labourer's sequence, using technical grade calcium hydroxide, the calcium hydroxide purity is 92-95%, silicon, magnesium, aluminium comprising 5-8% and a small amount of weight
Metal impurities are 7.5-8 with first acid for adjusting pH value after condensation reaction, bridging agent, sulfide precipitation agent are added in, in weak base
Property under the conditions of, make silicon, magnesium, aluminium and a small amount of beavy metal impurity precipitation, then remove impurity by filter plant, finally adjust pH
It is worth to 6-6.5.
Bridging agent is by formaldehyde and dicyandiamide polycondensation, and ammonium chloride is the strong of high ionization degree as initiator and modifying agent polycondensation
The high molecular polymer of cationic quaternary amine salt form.After condensation, by building bridge, flocculating, precipitation reaction, filter operation, drop
The a large amount of calcium ash and heavy metal that low-shrinkage mixture calcium hydroxide is brought into.
Aforementioned related art, before《The preparation method of low ash content calcium method pentaerythrite》、《Improve calcium method season penta 4
The method of the calcareous amount of alcohol byproduct formic acid》Described in patent application document.
Neopentyl glycol preparation process of the present invention, full gear process mainly remove unreacted formaldehyde, the condensation liquid after removal of impurities
Enter distillation under pressure tower from top, control tower top pressure is in 0.15-0.18Mpa, and tower bottom pressure 0.18-0.20Mpa, it is extra to make
Formaldehyde discharged from top with vapor phase, the condensed dilute formaldehyde for becoming 2-5%, the dilute formaldehyde isolated prepares formaldehyde again.
Embodiment 7
The calcium method neopentyl glycol preparation process of the present embodiment, as different from Example 6：Condensation after removal of impurities, full gear
Liquid enters evaporization process, and evaporator vacuum level requirements reach -0.08Mpa, and evaporator uses elevating membrane forced-circulation evaporator, steams
It is evaporating column to send out device top；Neopentyl glycol and water rise to evaporating column in the form of steam state in evaporation process, through overhead condensation water spray
Afterwards, due to the two boiling point difference, neopentyl glycol is reentered in evaporating column, and the condensed device of water removes evaporator, dense so as to reach
The effect of contracting, calcium formate crystal detach substandard goods calcium formate after being precipitated.
Embodiment 8
The calcium method neopentyl glycol preparation process of the present embodiment, as different from Example 7：By distillation process, main profit
It is different from other impurities boiling point with neopentyl glycol, it carries out concentration cooling and prepares sheet neopentyl glycol：Keep destilling tower vacuum degree for-
Product is put into finished product kettle when pot temperature reaches 150-160 DEG C by 0.078MPa, and control crystallization temperature is 135-140 DEG C,
Vacuum degree is -0.086 MPa, switches another crystallizer when liquid level is 2/3, and major product neopentyl glycol cools down through steel band to be sliced
Packaging.
Claims (5)
1. a kind of calcium method neopentyl glycol preparation process uses isobutylaldehyde, formaldehyde as raw material, using calcium hydroxide as catalyst and reaction
Object, by being condensed, evaporating, distillation process prepares neopentyl glycol, and in the condensation process, isobutylaldehyde, formaldehyde feed intake a kilogram volume
Than being 1:1.5-2.0；Molar ratio is isobutylaldehyde:Formaldehyde:Calcium hydroxide=1:2.5-3.5:0.58-0.65；The raw material is dense
It is 20-25%, concentration of formaldehyde 12-15%, calcium hydroxide 8-10% to spend for isobutylaldehyde；It is characterized in that：Process is condensed using such as
Under feeding mode：Formaldehyde is disposably put into, and isobutylaldehyde at the uniform velocity adds in, and calcium hydroxide uses technical grade hydrogen of the purity for 92-95%
Calcium oxide, silicon, magnesium, aluminium and a small amount of beavy metal impurity comprising 5-8%, feed intake for 3-10 minutes in advance and program is put into, i.e. first half term
The 1/4 of total amount is added in, the second half adds in the 3/4 of total amount, and is finished simultaneously with isobutylaldehyde；Setting-up point is controlled in 35-55
DEG C, the reaction time is 3-5 hours；After reaction, with first acid for adjusting pH value, bridging agent and sulfide precipitation agent are added in, weak
Under alkaline condition, make silicon, magnesium, aluminium and a small amount of beavy metal impurity precipitation, then remove impurity by filter plant；PH is adjusted again
Value removes formaldehyde excessive in condensation liquid by pressurizing tower, and full gear liquid enters evaporator, and dilute formaldehyde returns to condensation dispensing；Evaporation
Neopentyl glycol and water rise to evaporating column in the form of steam state in the process, after overhead condensation water spray, since the two boiling point is different, newly
Pentanediol is reentered in evaporating column, and the condensed device of water removes evaporating column, and so as to achieve the effect that concentration, calcium formate crystal is precipitated
Crystallization crystallization in motion device is put by leg is eluriated, so as to obtain high-quality byproduct calcium formate；Evaporation liquid is further concentrated through destilling tower,
Most neopentyl glycol finished product is sliced into through cooling afterwards.
2. calcium method neopentyl glycol preparation process according to claim 1, it is characterised in that：It is 7-8 that pH value is adjusted after condensation,
The sulfide precipitation agent is Ca2S, dosage are the 10-20ppm of liquor capacity, using principle is precipitated, make to be slightly soluble in water
Heavy metal forms extremely difficult molten sulfide；The bridging agent is formaldehyde and dicyandiamide polycondensation, as catalyst and is changed by the use of ammonium chloride
Property agent, molar ratio 2.3:1:0.63, the cation superpolymer with quaternary amine base of generation utilizes the hydrogen bond molecule of quaternary ammonium group
The Mg (OH) of water is insoluble in intermolecular forces, with condensation liquid2、Na2SiO3、Al(OH)3And other heavy metal sulfides are built bridge, shape
Into larger floc sedimentation, convenient for settling and filtering, dosage is the 3-6ppm of liquor capacity；The calcium formate crystallizes crystallization in motion device
Complete set of equipments, using calcium formate and the different solubility of neopentyl glycol, by acceleration of gravity, classification increases calcium formate crystalline substance paddle
Than so as to obtain the byproduct of high-quality.
3. calcium method neopentyl glycol preparation process according to claim 1, it is characterised in that：Including the process that cleans, using work
Industry grade calcium hydroxide, the calcium hydroxide purity are 92-95%, and silicon, magnesium, aluminium and a small amount of beavy metal impurity comprising 5-8% are condensed
After reaction, it is 7.5-8 with first acid for adjusting pH value, then adds in bridging agent, sulfide precipitation agent, under weak basic condition,
Make silicon, magnesium, aluminium and a small amount of beavy metal impurity precipitation, then remove impurity by filter plant, finally adjust pH value to 6-
6.5。
4. the calcium method neopentyl glycol preparation process according to claim 1,2 or 3, it is characterised in that：After removal of impurities, full gear
Condensation liquid enters evaporization process, and evaporator vacuum level requirements reach -0.08MPa, and evaporator uses elevating membrane forced-circulation evaporation
Device, evaporator top are evaporating columns；Neopentyl glycol and water rise to evaporating column in the form of steam state in evaporation process, through overhead condensation water
After spray, due to the two boiling point difference, neopentyl glycol is reentered in evaporating column, and the condensed device of water removes evaporator, so as to reach
To the effect of concentration, calcium formate crystal detaches substandard goods calcium formate after being precipitated.
5. calcium method neopentyl glycol preparation process according to claim 4, it is characterised in that：By distillation process, main profit
It is different from other impurities boiling point with neopentyl glycol, it carries out concentration cooling and prepares sheet neopentyl glycol：Keep destilling tower vacuum degree for-
Product is put into finished product kettle when pot temperature reaches 150-160 DEG C by 0.078MPa, and control crystallization temperature is 135-140 DEG C,
Vacuum degree is -0.086MPa, switches another crystallizer when liquid level is 2/3, and major product neopentyl glycol cools down through steel band to be sliced
Packaging.
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| EP3315484B1 (en) * | 2016-10-25 | 2019-02-27 | OXEA GmbH | Method for co-production of polyols in the presence of an inorganic base |
| CN109320397A (en) * | 2018-11-22 | 2019-02-12 | 湖南湘硕化工有限公司 | A kind of preparation method of neopentyl glycol |
| CN111393260B (en) * | 2020-04-29 | 2024-03-26 | 青岛科技大学 | Neopentyl glycol preparation process and equipment used in process |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102701908A (en) * | 2012-06-28 | 2012-10-03 | 衡阳师范学院 | Process for preparing neopentyl glycol with calcium method |
| CN103012059A (en) * | 2012-12-27 | 2013-04-03 | 衡阳师范学院 | Novel process for reducing consumption of formaldehyde in production of neopentyl glycol |
| CN104672060A (en) * | 2014-12-24 | 2015-06-03 | 保定市国秀化工有限责任公司 | Method for preparing pentaerythritol through low-ash calcium method |
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| DE102008031338B4 (en) * | 2008-07-02 | 2012-09-13 | Oxea Gmbh | Process for the preparation of neopentyl glycol |
| CN204337818U (en) * | 2014-12-24 | 2015-05-20 | 保定市国秀化工有限责任公司 | Calcium formate crystallization crystallization in motion complete set of equipments |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102701908A (en) * | 2012-06-28 | 2012-10-03 | 衡阳师范学院 | Process for preparing neopentyl glycol with calcium method |
| CN103012059A (en) * | 2012-12-27 | 2013-04-03 | 衡阳师范学院 | Novel process for reducing consumption of formaldehyde in production of neopentyl glycol |
| CN104672060A (en) * | 2014-12-24 | 2015-06-03 | 保定市国秀化工有限责任公司 | Method for preparing pentaerythritol through low-ash calcium method |
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