CN107973701A - The method of hydrofinishing polyester grade ethylene glycol - Google Patents
The method of hydrofinishing polyester grade ethylene glycol Download PDFInfo
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- CN107973701A CN107973701A CN201610939665.8A CN201610939665A CN107973701A CN 107973701 A CN107973701 A CN 107973701A CN 201610939665 A CN201610939665 A CN 201610939665A CN 107973701 A CN107973701 A CN 107973701A
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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
- C07C29/88—Separation; Purification; Use of additives, e.g. for stabilisation by treatment giving rise to a chemical modification of at least one compound
- C07C29/90—Separation; Purification; Use of additives, e.g. for stabilisation by treatment giving rise to a chemical modification of at least one compound using hydrogen only
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J25/00—Catalysts of the Raney type
- B01J25/02—Raney nickel
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The present invention provides a kind of method of hydrofinishing polyester grade ethylene glycol, and this method includes hydrogenation technique and hydrogenation Posterior circle technique；In hydrogenation technique, the contact of composite hydrogenation catalyst, hydrogen and ethylene glycol crude product is reacted, obtains product stream；In Posterior circle technique is hydrogenated with, 40%~95% product stream is returned into hydrogenation technique；The composite hydrogenation catalyst includes：Continuous phase carbon, dispersed phase Raney alloy particle, wherein dispersed phase Raney alloy uniform particle or are non-uniformly dispersed in continuous phase carbon, and the continuous phase carbon is obtained after organic matter or the carbonization of its mixture by that can be carbonized.After present invention process is hydrogenated with upgrading, polyester grade ethylene glycol can obtain；Realize and adjust ethylene glycol product yield and product quality indicator.
Description
Technical field
The present invention relates to hydrofinishing ethylene glycol field, more particularly, to a kind of hydrofinishing polyester grade ethylene glycol
Method.
Background technology
Ethylene glycol is a kind of important industrial chemicals, widely used, can be used as the raw material of antifreezing agent and polyester fiber.Second two
Alcohol can arbitrarily be mixed with water, and boiling point is high, solidification point is low, is very common antifreezing agent, important be organised as a kind of
Work raw material, ethylene glycol should be prepared in polyester slice, various anti-icing fluid, cooling agent, rosin ester, drier, softening agent etc. extensively
Field.
Ethylene glycol accounts for more than the 90% of total amount mainly for the production of polyester and motor vehicle antifreeze fluid, the ethylene glycol of the two consumption,
Wherein polyester accounts for 79.5%, and anti-icing fluid accounts for 12.4%.When ethylene glycol is used to produce polyester slice, the requirement to material purity is more
Height, is about set to " top grade product " ethylene glycol in national standard.In the quality standard of " top grade product " ethylene glycol, there is a ultraviolet printing opacity
Rate index (UV values), respectively measures the ultraviolet light of 350nm wavelength, 275nm wavelength and 220nm wavelength.Ethylene glycol product
Present in low content, should not the impurity that goes out of conventional detection it is different to the degree of absorption of these three wavelength lights, so ultraviolet printing opacity
Rate can accurately reflect the impurity content of ethylene glycol product, the clear stipulaties controlling value of the index in national standard.
Due to the difference of ethylene glycol production technology route, dopant species are also very much, but the influence that everybody generally accepts at present
The main matter of product UV values is configured to the compound containing carbonyl or conjugated double bond.This unsaturated compounds has at 220nm
Relatively strong to absorb, therefore, the UV transmittance of glycol sample can represent the purity of ethylene glycol to a certain extent at 220nm.
In order to improve the quality of ethylene glycol product, the method for improving ethylene glycol purity is continuously developed out, at present second two
The technology of alcohol purification is broadly divided into absorption method and deep hydrogenation method.
Absorption method is the method for everybody prevalence in recent years, and feature is that technique is simple, investment is low, is to utilize adsorbent
Suction-operated is selected by the impurity removal in ethylene glycol, so as to fulfill the raising of product UV values.Patent of the PPG companies in 1976
In just point out that activated carbon (AC) can adsorb the unsaturated compound in ethylene glycol, significantly improve the UV light transmittances of ethylene glycol.Specially
Sharp document WO9958483 and US3971711 describes one kind and purifies organic liquid with activated carbon respectively, particularly the side of alcohol
Method, can improve the UV transmittance of alcohol, while will not significantly improve its pH value.But also studies have pointed out that because of material charcoal
Property is not active enough, and is difficult to change, therefore not high to the selectivity of unsaturated compound absorption.Nanjing University of Technology Zhang Yongbin
The influence to ethylene glycol product UV values is have studied using NY type homogeneous catalysts, research is found, can under certain process conditions
So that the ethylene glycol of production reaches the advanced standard of SD companies of U.S. chemical fiber grade.Since ion exchange resin is a kind of surface functional group
Can modulation sorbing material, can realize the selective absorption of impurity using the modulation of surface zwitterion.American documentation literature
US6187973 is reported to be handled using anion exchange data, and it is with exchanged strong of sulphite that they are selected
Alkaline anion exchange number fat, its main purpose are to remove aldehyde, while can also reach the effect for improving ethylene glycol UV transmittance.State
Interior existing dealdehyding resin producer is mainly Jiangsu Su Qing water process company and Kai Rui chemical industry, is by ion exchange resin
Suction-operated, adsorbs the making choice property of unsaturated compound in thick ethylene glycol, so as to improve the UV values of product.Although absorption
Method can improve the UV values of product, but due to the absorption total amount and one way limited sorption capacity of adsorbent, so to ethylene glycol
The lifting degree of product UV values is relatively low, and controlled range is relatively narrow, for the relatively low ethylene glycol product scarce capacity of processing UV values.
American documentation literature US4289593 is described one kind and technical grade ethylene glycol is shone using ultraviolet light emission source
Penetrate, the method for making up to fibre-grade standard.For irradiation light wavelength at least will in 220nm, preferably higher than 240nm,
Ethylene glycol light transmittance under 220nm, 275nm and 350nm wave number significantly improves after irradiation.
American documentation literature US43494171 is reported a kind of improves the method for UV transmittance of ethylene glycol by adding alkali.With this side
Ethylene glycol purity made from method is high, is higher than 70% in the UV transmittance of 220nm, the alkali metal compound of addition is not also to rear
The purification apparatus of system impacts.The additive of another patent document US4358625 report is the boron hydride of alkali metal,
Boron hydride is added before or after ethylene oxide fills water, most common is to add NaBH4, what is added can be solid
The solution of body or stabilization；The ethylene glycol product UV that raw material produces after treatment has been worth to effective raising, reaches
The level of polyester grade.Patent document US5440058 points out active, usually opposite there is volatile organic or inorganic chemical combination
Thing, when they are formed as accessory substance, can be removed, if changing into salt again by the way that they are converted into low-volatile material
The means such as distillation, extracting, UF membrane or Solid Bed can be used to remove；They are carbon containing to remove with the method for addition sodium hydrogensulfite
The impurity of base, such as aldehyde and ketone.European patent document EP310189 describes a kind of method for purifying ethylene glycol, is to use the second light industry bureau base
Oxalic Acid Method produces ethylene glycol.Ethylene glycol is distilled under the conditions of PH=7.5, can remove influences ethylene glycol UV transmittance
Impurity, reach fibre-grade standard.
In short, cause to produce because containing unsaturated compounds such as micro carboxylic acid, aldehydes, conjugation olefine aldehydrs in ethylene glycol product
Product are relatively low in the UV transmittance of 220-350nm scopes, influence the quality of downstream product polyester.In order to improve the ultraviolet of ethylene glycol
Light transmittance by certain method, it is necessary to remove micro unsaturates, so as to improve the UV transmittance of ethylene glycol product.
In industrial production, polyester grade ethylene glycol is the main application of ethylene glycol, and polyester grade ethylene glycol is to product purity
It is it is required that very high, it is necessary to reach high-class product ethylene glycol.But in petrochemical industry route, because various conditions cause product quality not
Stablize, or even have that part ethylene glycol product is fine in appearance, but its UV transmittance (220nm) be in 1.0~5.0% it
Between, and the polyester grade ethylene glycol index needs to be more than 75%, even more high.
The content of the invention
The purpose of the present invention is for the unstable product quality caused by various conditions in existing ethylene glycol production technology
Problem, there is provided a kind of method of hydrofinishing polyester grade ethylene glycol, after being hydrogenated with upgrading, can obtain polyester grade ethylene glycol；It is real
Now adjust ethylene glycol product yield and product quality indicator.
To achieve these goals, the present invention provides a kind of method of hydrofinishing polyester grade ethylene glycol, and this method includes
Hydrogenation technique and hydrogenation Posterior circle technique；
In hydrogenation technique, the contact of composite hydrogenation catalyst, hydrogen and ethylene glycol crude product is reacted, obtains product
Stream；In Posterior circle technique is hydrogenated with, 40%~95% product stream is returned into hydrogenation technique；
The composite hydrogenation catalyst includes：Continuous phase carbon, dispersed phase Raney alloy particle, wherein dispersed phase thunder Buddhist nun close
Gold particle is evenly or uniformly dispersed in continuous phase carbon, and the continuous phase carbon is the organic matter or its mixture by that can be carbonized
Obtained after carbonization.
Obtained product stream in hydrogenation technique after hydrogenation reaction has been qualified product stream, the product thing
Material returns to hydrogenation technique, refers to that a portion of products therefrom material after hydrogenation reactor is reacted returns to hydrogenation reaction
Device, mixes latter with fresh not hydrogenated reaction raw materials and enters hydrogenation reactor.The purpose for returning to technique is former to reaction
Material plays the role of diluted, the impurity content of influence quality of glycol in reduction reaction raw materials, after operating is stablized, hydrofinishing
Ethylene glycol product more easily reachs the requirement of polyester grade.
The method provided according to the present invention, it is preferable that the condition of the hydrogenation technique includes：Reaction temperature for 50 DEG C~
200 DEG C, reaction pressure is 0.1~8.0MPa, using the reaction velocity of the liquid volume metering of ethylene glycol crude product as 0.05~20h-1,
The volume ratio of hydrogen and ethylene glycol crude product is 200~10000:1；Preferable reaction temperature is 80 DEG C~120 DEG C, and reaction pressure is
0.2~2.0MPa, using the reaction velocity of the liquid volume metering of ethylene glycol crude product as 0.1~6.0h-1, hydrogen and ethylene glycol crude product
Volume ratio be 600~2000:1.
The method provided according to the present invention, it is preferable that in the hydrogenation Posterior circle technique, by the first of 80%~95%
Stream returns to hydrogenation technique.
The method provided according to the present invention, the organic matter that can be carbonized refer to：Being handled under certain temperature, atmospheric condition has
Machine thing, hydrogen, oxygen, nitrogen, sulphur in organic matter etc. is all or big portion vapors away, so as to obtain a kind of very high synthesis material of phosphorus content
Material, obtained carbon material have the performance such as high temperature resistant, high intensity, high-modulus, porous.
The organic matter that can be carbonized is in organic high molecular compound, coal, bitumen, asphalt and coal tar pitch
It is at least one.Preferably, the organic matter being carbonized is organic high molecular compound, and the organic high molecular compound includes
Natural organic polymer compounds and synthetic organic polymer compound；The natural organic polymer compounds are preferably to form sediment
At least one of powder, viscose rayon, lignin and cellulose；The synthetic organic polymer compound be preferably plastics and/
Or rubber, more preferably epoxy resin, phenolic resin, furane resins, polystyrene, styrene-divinylbenzene copolymer,
At least one of polyacrylonitrile, butadiene-styrene rubber and polyurethane rubber.
The method provided according to the present invention, it is preferable that Raney alloy particle includes Raney metal and the element that can be leached.
" Raney metal " metal insoluble when referring to be activated with Lei Nifa, the Raney metal in nickel, cobalt, copper and iron at least one
Kind.The element that " element that can be leached " can be dissolved when referring to be activated with Lei Nifa, the element that can be leached be selected from aluminium, zinc and
At least one of silicon.Raney alloy particle is selected from nickel alumin(i)um alloy, cobalt aluminium alloy or albronze, is preferably nickel alumin(i)um alloy.
In Raney alloy particle, the weight ratio of Raney metal and the element that can be leached is 1：99~10：1, preferred scope 1：10~
4：1.The average grain diameter of the Raney alloy particle is generally 0.1~1000 micron, is preferably 10~100 microns.
The method provided according to the present invention, in order to improve catalyst activity or selectivity, the Raney alloy particle is also
Including accelerating agent, the amount of the accelerating agent accounts for 0.01wt%~5wt% of the Raney alloy particle total amount；The accelerating agent choosing
From at least one of Mo, Cr, Ti, Fe, Pt, Pd, Rh and Ru.
The method provided according to the present invention, it is preferable that the preparation method of the composite hydrogenation catalyst is：It can be carbonized
Organic matter mixed with Raney alloy particle after carry out molded curing and high temperature cabonization, obtain continuous phase carbon and Raney alloy particle
Compound.
It is further preferred that the preparation method of the composite catalyst comprises the following steps：
A, the organic matter that can be carbonized is mixed with additive, prepares curing system；
B, Raney alloy particle is uniformly mixed with the curing system, then molded curing, obtains catalyst precarsor；
C, under inert gas shielding, the 400-1900 DEG C of carbonization catalyst precarsor；
In step a, it is often to use curing formula according to the organic matter that can be carbonized to prepare curing system, and the additive is selected from
Curing accelerator, dyestuff, pigment, colouring agent, antioxidant, stabilizer, plasticizer, lubricant, flow ability modifying agent or auxiliary agent, resistance
Fire in agent, dripping inhibitor, anti-caking agent, adhesion promoter, conductive agent, polyvalent metal ion, impact modifying agent, demolding aids and nucleator
At least one.Additive therefor dosage is conventional amount used, or is adjusted according to the requirement of actual conditions.The curing of preparation
System is liquid system or powdery system, and liquid system can be stirred evenly directly；Powdery system can directly be blended uniformly；Coccoid
The available industrial common any disintegrating apparatus of system is blended uniform after crushing.
In stepb, the weight ratio of the Raney alloy particle and the organic matter that can be carbonized is 1：99~99：1, be preferably
10：90~90：10, more preferably 25：75~75：25.Obtained catalyst precarsor can use any available organic high score
Sub- material processing plant, by cutting, cutting, punching press or it is broken the methods of be processed into fixed bed or fluidized-bed reaction and can make
Particle, the particle size of particle is can meet that particle size is base needed for fixed bed catalyst or fluid catalyst
Standard, the shape of particle may be selected from any irregular shape, orbicule, hemispherical mass, cylinder, semi-cylindrical body, prism-shaped
Combination of body, cube, cuboid, ring bodies, half-annuli, hollow cylinder, tooth form or more shape etc., preferably spherical,
At least one of annular, tooth form and cylinder.
In step c, the carbonization carries out generally in tubular heater, and carbonization operation temperature is generally 400-1900
DEG C, preferably 600-950 DEG C, protective gas is the inert gases such as nitrogen or argon gas, when carbonization 1-12 is small.For example, phenolic resin
When 850 DEG C of carbonizations 3 are small, you can carbonization, forms porous carbon.Higher carburizing temperature can cause the carbon obtained after carbonization
It is more regular.
The method provided according to the present invention, it is preferable that the composite hydrogenation catalyst is the catalyst after activation process,
The step of activation process, includes：At 25 DEG C~95 DEG C, with the aqueous slkali that concentration is 0.5~30wt% to described compound
Hydrogenation catalyst carries out activation process；It is further preferred that aqueous slkali is NaOH or KOH, the activation process time for 5 minutes~
72 it is small when.
By controlling the addition of Raney alloy particle and/or the activation journey of control catalyst in catalyst preparation process
Degree, so as to easily control the load capacity of Raney metal in catalyst, such as can obtain Raney metal load capacity as 1
Catalyst after the activation of~90wt% (being counted using overall catalyst weight as 100%), preferably Raney metal load capacity for 10~
Catalyst after the activation of 80wt%, more preferably Raney metal load capacity are 40~80wt%.
The present invention is carbonized after the organic matter that can be carbonized is mixed with Raney alloy particle, obtains carbon and Raney alloy grain
The compound of son, Raney alloy particle play facilitation to carbonisation, carbonization can be made to carry out more complete, are carbonized
Afterwards, Raney alloy particle is dispersed in the continuous phase of carbon, and has porous knot with continuous phase carbon strong bonded, continuous phase carbon itself
Structure, makes gained catalyst have very high intensity.Meanwhile Raney alloy particle distribution, in the gap of carbon, solution or gas can
To easily touch Raney alloy, composite catalyst is soaked with lye, it is more that Raney alloy particle obtains activation formation
The high activity Raney metal in hole, while a small amount of agraphitic carbon is also washed away, continuous phase carbon material is able to reaming, more thunder Buddhist nuns
Alloy particle is exposed, so that catalyst has very high activity.
The beneficial effects of the present invention are：Our used catalyst product impurity is few, active metal load capacity is high, catalysis
Agent granule strength is good, and it is high that it is used for activity during hydrofining reaction；Use high activity composite hydrogenation catalyst for refining and hydrogenation
Product circulation technology is combined afterwards, can significantly improve the UV transmittance of ethylene glycol, reaches the matter of polyester grade ethylene glycol
Amount requires.
Embodiment
The preferred embodiment of the present invention is more fully described below with reference to embodiment.Although this is described in embodiment
The preferred embodiment of invention, however, it is to be appreciated that may be realized in various forms the reality of the invention without that should be illustrated here
The mode of applying is limited.
According to Lambert-Beer's law, its absorbance (A) is directly proportional to the product of solution liquid layer thickness (b) and concentration (c),
That is A=kbc, A=-lgT.The absorptivity of material is constant under Same Wavelength.In addition from ultraviolet spectra principle, pure second
Glycol more than wavelength 200nm without absorption, so concentration c can be approximately the total concentration of such impurity, by lgT and impurity total concentration
C is linear that removal of impurity is：
Note：X：Removal of impurity；c0：The impurity concentration of raw material；c1：Impurity concentration after hydrogenation；T0：The ultraviolet printing opacity of raw material
Rate；T1：UV transmittance after hydrogenation.
Industrial spent glycol national standard (GB/T4649-2008) is to the UV transmittance of high-class product ethylene glycol product
It is it is required that as follows：
220nm is more than or equal to 75%
275nm is more than or equal to 92%
350nm is more than or equal to 99%.
The present invention wants the ethylene glycol raw material UV transmittance index of hydrofinishing to be：220nm 0.5~5%, 275nm
20~70%, 350nm 40~99%, appearance transparent is colourless.
Preparation example
Prepare composite hydrogenation catalyst CAT-1：
(1) by liquid-state epoxy resin (Ba Ling petrochemical industry, CYD-128) 100 mass parts, curing agent methyl tetrahydro phthalic anhydride
(MeTHPA) (the Guangdong flourishing age reaches science and trade limited company) 85 mass parts, curing accelerator triethanolamine (TEA) (Tianjin
Learn reagent one factory) 1.5 mass parts stir evenly；
(2) epoxy curing systems prepared in 40g steps (1) are weighed and 180g Nickel Aluminium Alloy Powders are thoroughly mixed, nickel
Ni contents are 48wt% in aluminium alloy, and aluminium content 52wt%, takes appropriate mixture to be added in cylindrical die, use compression molding
Instrument is molded 30mins under conditions of 120 DEG C of temperature, pressure 7MPa, with compression molding instrument in 150 DEG C of temperature, the bar of pressure 7MPa
90mins is molded under part, cooling is taken out, that is, obtains granular catalyst precarsor；
(3) 100ml catalyst precarsors are measured, are put into tubular type high-temperature electric resistance furnace, 10 DEG C/min of heating rate, carburizing temperature
600 DEG C, when holding 3 is small, nitrogen protection, nitrogen flow 200ml/min, i.e. obtained catalyst after nitrogen protection cooling；
(4) 20%NaOH aqueous solution 400g are configured with deionized water, adds catalyst 50ml obtained by step (3), keep temperature
85 DEG C of degree, 4 it is small when after filter out solution, that is, the composite catalyst activated, nickel content of metal is about in final catalyst
For 60wt%, wash to close to after neutrality, deposit in spare in deionized water.
Embodiment 1
By ethylene glycol liquid by fixed bed reactors hydrofinishing, composite hydrogenation catalyst CAT-150ml is loaded
Fixed bed reactors, bore 25mm, hydrogen flowing quantity 200ml/min, 100 DEG C, pressure 0.5MPa of reaction temperature, ethylene glycol liquid
Air speed 6.0h-1；Raw material UV transmittance before hydrogenation：220nm 2.6%, 275nm 50%, 350nm 76%, product returns after hydrogenation
The ratio of returning is 95%, and product is shown in Table 1 using ultraviolet specrophotometer measure UV transmittance after hydrogenation.
Embodiment 2
According to the method hydrofinishing ethylene glycol of embodiment 1, difference is, product return ratio is after hydrogenation
90%；Raw material UV transmittance before hydrogenation：220nm 2.6%, 275nm 50%, 350nm 76%, product uses purple after hydrogenation
Outer spectrophotometric determination UV transmittance is shown in Table 1.
Embodiment 3
According to the method hydrofinishing ethylene glycol of embodiment 1, difference is, product return ratio is after hydrogenation
80%；Raw material UV transmittance before hydrogenation：220nm 2.6%, 275nm 50%, 350nm 76%, product uses purple after hydrogenation
Outer spectrophotometric determination UV transmittance is shown in Table 1.
Embodiment 4
According to the method hydrofinishing ethylene glycol of embodiment 1, difference is, product return ratio is after hydrogenation
40%；Raw material UV transmittance before hydrogenation：220nm 2.6%, 275nm 50%, 350nm 76%, product uses purple after hydrogenation
Outer spectrophotometric determination UV transmittance is shown in Table 1.
Embodiment 5
According to the method hydrofinishing ethylene glycol of embodiment 3, difference is, composite hydrogenation catalyst CAT-1 is used
Measure as 100ml；Product is shown in Table 1 using ultraviolet specrophotometer measure UV transmittance after hydrogenation.
Embodiment 6
According to the method hydrofinishing ethylene glycol of embodiment 3, difference is, composite hydrogenation catalyst CAT-1 is used
Measure as 200ml；Product is shown in Table 1 using ultraviolet specrophotometer measure UV transmittance after hydrogenation.
Comparative example 1
According to the method hydrofinishing ethylene glycol of embodiment 1, difference is that product does not return after hydrogenation；Before hydrogenation
Raw material UV transmittance：220nm 2.6%, 275nm 50%, 350nm 76%, product uses ultraviolet specrophotometer after hydrogenation
Measure UV transmittance is shown in Table 1.
Comparative example 2
According to the method hydrofinishing ethylene glycol of embodiment 3, difference is that product does not return after hydrogenation, and reacts
Raw material ethylene glycol liquid air speed is by 6.0h-1It is reduced to 1.2h-1；Raw material UV transmittance before hydrogenation：220nm 2.6%, 275nm
50%, 350nm 76%, product is shown in Table 1 using ultraviolet specrophotometer measure UV transmittance after hydrogenation.
Comparative example 3
According to the method hydrofinishing ethylene glycol of embodiment 1, difference is that unifining process used catalyst is
The nickel-metal catalyst of alumina load, dosage are same as Example 1.The nickel-metal catalyst of alumina load passes through pressed disc method
Prepare：First by 1kg basic nickel carbonates NiCO3·2Ni(OH)2·4H2O is with after a certain amount of boehmite kneading, drying, roasting
Burn, be granulated, compression molding is Φ 3mm × 3mm cylindrical catalyst particles, reduces the metal of nickel containing 56wt% in rear catalyst, is used
Reacted in fixed bed hydrogenation.Product is shown in Table 1 using ultraviolet specrophotometer measure UV transmittance after hydrogenation.
The ethylene glycol product UV transmittance that 1 distinct methods of table obtain
Experiment conclusion：It can be seen that from the result of embodiment, product return ratio is higher after hydrogenation, and the effect of hydrofinishing is got over
Good, hydrogenation technique can be effectively by the ethylene glycol product that ethylene glycol hydrofinishing is purity higher, even polyester grade second two
Alcohol product；With the composite hydrogenation catalyst for being not provided with the comparative example 1-2 of return to step and not using the present invention to prepare
Comparative example 3 compare, the hydrogenation technique that uses of the present invention, refines the better of purification ethylene glycol product.
Various embodiments of the present invention are described above, described above is exemplary, and non-exclusive, and
It is not limited to disclosed each embodiment.In the case of without departing from the scope and spirit of illustrated each embodiment, for this skill
Many modifications and changes will be apparent from for the those of ordinary skill in art field.
Claims (10)
- A kind of 1. method of hydrofinishing polyester grade ethylene glycol, it is characterised in that this method is followed after including hydrogenation technique and hydrogenation Ring technique；In hydrogenation technique, the contact of composite hydrogenation catalyst, hydrogen and ethylene glycol crude product is reacted, obtains product material Stream；In Posterior circle technique is hydrogenated with, 40%~95% product stream is returned into hydrogenation technique；The composite hydrogenation catalyst includes：Continuous phase carbon, wherein dispersed phase Raney alloy particle, dispersed phase Raney alloy grain Son is evenly or uniformly dispersed in continuous phase carbon, and the continuous phase carbon is the organic matter or the carbonization of its mixture by that can be carbonized Obtain afterwards.
- 2. the method for hydrofinishing polyester grade ethylene glycol according to claim 1, wherein,The condition of the hydrogenation technique includes：Reaction temperature is 50 DEG C~200 DEG C, and reaction pressure is 0.1~8.0MPa, with second two The reaction velocity of the liquid volume metering of alcohol crude product is 0.05~20h-1, the volume ratio of hydrogen and ethylene glycol crude product for 200~ 10000:1；Preferable reaction temperature is 80 DEG C~120 DEG C, and reaction pressure is 0.2~2.0MPa, with the liquid body of ethylene glycol crude product The reaction velocity of product metering is 0.1~6.0h-1, the volume ratio of hydrogen and ethylene glycol crude product is 600~2000:1.
- 3. the method for hydrofinishing polyester grade ethylene glycol according to claim 1, wherein,In the hydrogenation Posterior circle technique, 80%~95% first stream is returned into hydrogenation technique.
- 4. the method for hydrofinishing polyester grade ethylene glycol according to claim 1, wherein,The organic matter being carbonized is organic high molecular compound, and the organic high molecular compound includes natural organic high score Sub- compound and synthetic organic polymer compound；The natural organic polymer compounds are preferably starch, viscose rayon, wood At least one of quality and cellulose；The synthetic organic polymer compound is preferably plastics and/or rubber, further excellent Elect epoxy resin, phenolic resin, furane resins, polystyrene, styrene-divinylbenzene copolymer, polyacrylonitrile, butylbenzene rubber as At least one of glue and polyurethane rubber.
- 5. the method for hydrofinishing polyester grade ethylene glycol according to claim 1, wherein,The preparation method of the composite hydrogenation catalyst is：Carried out after the organic matter that can be carbonized is mixed with Raney alloy particle Molded curing and high temperature cabonization, obtain the compound of continuous phase carbon and Raney alloy particle.
- 6. the method for hydrofinishing polyester grade ethylene glycol according to claim 5, wherein,The preparation method of the composite catalyst comprises the following steps：A, the organic matter that can be carbonized is mixed with additive, prepares curing system；B, Raney alloy particle is uniformly mixed with the curing system, then molded curing, obtains catalyst precarsor；C, under inert gas shielding, the 400-1900 DEG C of carbonization catalyst precarsor；The additive be selected from curing accelerator, dyestuff, pigment, colouring agent, antioxidant, stabilizer, plasticizer, lubricant, It is flow ability modifying agent or auxiliary agent, fire retardant, dripping inhibitor, anti-caking agent, adhesion promoter, conductive agent, polyvalent metal ion, impact modified At least one of agent, demolding aids and nucleator.
- 7. the method for hydrofinishing polyester grade ethylene glycol according to claim 5, wherein,The weight ratio of Raney alloy particle and the organic matter that can be carbonized is 1：99~99：1, it is preferably 10：90~90：10, it is more excellent Elect 25 as：75~75：25.
- 8. the method for hydrofinishing polyester grade ethylene glycol according to claim 1, wherein,Raney alloy particle includes the weight ratio of Raney metal and the element that can be leached, Raney metal and the element that can be leached For 1：99~10：1, it is preferably 1：10~4：1, the Raney metal is selected from least one of nickel, cobalt, copper and iron, it is described can The element being leached is selected from least one of aluminium, zinc and silicon.
- 9. the method for the hydrofinishing polyester grade ethylene glycol according to any one of claim 1-8, wherein, Raney alloy grain Son further includes accelerating agent, and the amount of the accelerating agent accounts for 0.01wt%~5wt% of Raney alloy particle total amount；The accelerating agent choosing From at least one of Mo, Cr, Ti, Fe, Pt, Pd, Rh and Ru.
- 10. the method for the hydrofinishing polyester grade ethylene glycol according to any one of claim 1-8, wherein, it is described compound Type hydrogenation catalyst is the catalyst after activation process, and the step of activation process includes：At 25 DEG C~95 DEG C, concentration is used Activation process is carried out to the composite hydrogenation catalyst for the aqueous slkali of 0.5~30wt%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610939665.8A CN107973701B (en) | 2016-10-25 | 2016-10-25 | Method for hydrofining polyester-grade ethylene glycol |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111644172A (en) * | 2019-09-09 | 2020-09-11 | 上海浦景化工技术股份有限公司 | Catalyst for liquid phase hydrogenation and preparation method and application thereof |
| CN111662162A (en) * | 2020-05-23 | 2020-09-15 | 安阳化学工业集团有限责任公司 | Additive for improving ultraviolet transmittance of coal-made glycol and method for preparing polyester-grade glycol by using additive |
| CN112174780A (en) * | 2020-09-27 | 2021-01-05 | 吉化集团油脂化工有限公司 | Control method for improving UV value of ethylene glycol product through low-pressure catalytic hydrogenation |
| CN116041146A (en) * | 2022-12-19 | 2023-05-02 | 常州大学 | Glycol hydrofining method and equipment |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111644172A (en) * | 2019-09-09 | 2020-09-11 | 上海浦景化工技术股份有限公司 | Catalyst for liquid phase hydrogenation and preparation method and application thereof |
| CN111644172B (en) * | 2019-09-09 | 2023-12-01 | 上海浦景化工技术股份有限公司 | Catalyst for liquid phase hydrogenation and preparation method and application thereof |
| CN111662162A (en) * | 2020-05-23 | 2020-09-15 | 安阳化学工业集团有限责任公司 | Additive for improving ultraviolet transmittance of coal-made glycol and method for preparing polyester-grade glycol by using additive |
| CN111662162B (en) * | 2020-05-23 | 2022-08-12 | 安阳化学工业集团有限责任公司 | Additive for improving ultraviolet transmittance of coal-made glycol and method for preparing polyester-grade glycol by using additive |
| CN112174780A (en) * | 2020-09-27 | 2021-01-05 | 吉化集团油脂化工有限公司 | Control method for improving UV value of ethylene glycol product through low-pressure catalytic hydrogenation |
| CN116041146A (en) * | 2022-12-19 | 2023-05-02 | 常州大学 | Glycol hydrofining method and equipment |
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