CN107973699A - The method of purifying ethylene glycol - Google Patents
The method of purifying ethylene glycol Download PDFInfo
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- CN107973699A CN107973699A CN201610935654.2A CN201610935654A CN107973699A CN 107973699 A CN107973699 A CN 107973699A CN 201610935654 A CN201610935654 A CN 201610935654A CN 107973699 A CN107973699 A CN 107973699A
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- ethylene glycol
- hydrogenation catalyst
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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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Abstract
The present invention provides a kind of method of purifying ethylene glycol, and this method comprises the following steps：The contact of composite hydrogenation catalyst, hydrogen, coconut husk charcoal and ethylene glycol crude product is reacted；The mass ratio of the coconut husk charcoal and the composite hydrogenation catalyst is 1:10~20:1, the gross mass of the coconut husk charcoal and composite hydrogenation catalyst is 1~10wt% of ethylene glycol crude product quality；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.The method of the present invention make it that ethylene glycol product treatment effeciency is high, processing equipment is simple, investment is small.
Description
Technical field
The present invention relates to ethylene glycol purifying technique field, more particularly, to a kind of method of purifying ethylene glycol.
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.Pointed out in patent document US5440058, it is active, usually opposite that there is volatile organic or nothing
Machine compound, when they are formed as accessory substance, can be removed again by the way that they are converted into low-volatile material.If turn
Being melted into salt can use the means such as distillation, extracting, UF membrane or Solid Bed to remove.They are removed with the method for addition sodium hydrogensulfite
Go containing carbon-based impurity, 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, it is ultraviolet that influence ethylene glycol can be removed
The impurity of light transmittance, reaches 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, the underproof situation of ethylene glycol product can be frequently present of, it is ultraviolet in order to improve ethylene glycol product
, it is necessary to invest relevant device, how low-cost high-efficiency handles ethylene glycol product, improves its quality light rate, is with economic value
's.
The content of the invention
The purpose of the present invention is for the defects of existing purifying ethylene glycol technology, there is provided a kind of side of purifying ethylene glycol
Method so that ethylene glycol product treatment effeciency is high, processing equipment is simple, investment is small.
To achieve these goals, the present invention provides a kind of method of purifying ethylene glycol, and this method comprises the following steps：
The contact of composite hydrogenation catalyst, hydrogen, coconut husk charcoal and ethylene glycol crude product is reacted；The coconut husk charcoal and institute
The mass ratio for stating composite hydrogenation catalyst is 1:10~20:1, the gross mass of the coconut husk charcoal and composite hydrogenation catalyst is
1~10wt% of ethylene glycol crude product quality；
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.
The method provided according to the present invention, it is preferable that the coconut husk charcoal and the mass ratio of the composite hydrogenation catalyst
For 1:5~10:1, more preferably 1:2~5:1.
The method provided according to the present invention, it is preferable that the coconut husk charcoal and the gross mass of composite hydrogenation catalyst are second
2~8wt% of glycol crude product quality, more preferably 3~5wt%.
The method provided according to the present invention, during purifying ethylene glycol, by composite hydrogenation catalyst, hydrogen, coconut husk
Charcoal and ethylene glycol crude product are added in batch reactor and are reacted.
The method provided according to the present invention, it is preferable that more preferably small for 5~24 when the reaction time is 0.5~48 small
When；Reaction temperature is preferably 50 DEG C~120 DEG C, more preferably 80 DEG C~100 DEG C；Hydrogen Vapor Pressure is preferably 0.1~20MPa, more
Preferably 0.3~2MPa.
The method provided according to the present invention, the concept that the coconut husk charcoal is known in the art, is that a kind of black is unformed
Shot-like particle, is formed, it belongs to one kind of activated carbon, with coconut husk is made and gains the name by coconut husk refining；In the present invention, the coconut husk
Charcoal can be commercially available, and preferably be used with pulverulence.
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 in organic matter, coal, bitumen, asphalt and the coal tar pitch that can be carbonized extremely
Few one kind.Preferably, the organic matter being carbonized is organic high molecular compound, and organic high molecular compound, which includes, naturally to be had
Machine high-molecular compound and synthetic organic polymer compound；The natural organic polymer compounds are preferably starch, viscose glue
At least one of fiber, lignin and cellulose；The synthetic organic polymer compound is preferably plastics and/or rubber,
More preferably epoxy resin, phenolic resin, furane resins, polystyrene, styrene-divinylbenzene copolymer, polypropylene
At least one of nitrile, butadiene-styrene rubber and polyurethane rubber.
The method provided according to the present invention, Raney alloy particle include Raney metal and the element that can be leached." Lei Nijin
Category " metal insoluble when referring to be activated with Lei Nifa, most typical Raney metal are at least one of nickel, cobalt, copper and iron.
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 generally 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, it is preferably 1:10~4:1.
The average grain diameter of Raney alloy particle is generally 0.1~1000 micron, is preferably 10~100 microns.
In order to improve catalyst activity or selectivity, the method provided according to the present invention, it is preferable that Raney alloy particle
Accelerating agent is further included, the amount of the accelerating agent accounts for 0.01wt%~5wt% of Raney alloy particle total amount；The accelerating agent is selected 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；
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,
More preferably 25:75~75:25.
It is further preferred that the preparation of composite hydrogenation catalyst comprises the following specific steps that：
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, 400~1900 DEG C of carbonization catalyst precarsors, are made the composite catalyst.
In step a, prepare curing system and curing formula is often used according to the organic matter that can be carbonized, when preparation, which can add, to be added
Add agent, 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.The dosage of additive therefor is conventional amount used, or according to actual conditions
It is required that it is adjusted.The curing system of preparation is liquid system or powdery system, and liquid system can be stirred evenly directly；Coccoid
System can directly be blended uniformly；Powdery system is blended uniform after being crushed by industrial common any disintegrating apparatus.
In stepb, the catalyst precarsor obtained can use any available high-molecular organic material process equipment, lead to
Cross cutting, cutting, punching press or it is broken the methods of be processed into fixed bed or fluid bed carries out the particle that reaction can use, particle
Particle size on the basis of it can meet particle size needed for fixed bed catalyst or fluid catalyst, the shape of particle
Can be any irregular shape, orbicule, hemispherical mass, cylinder, semi-cylindrical body, prism-shaped body, cube, rectangular
At least one of body, ring bodies, half-annuli, hollow cylinder and tooth form, preferably spherical, annular, tooth form and cylinder
At least one of.
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 aldehyde
Resin is when 850 DEG C of carbonizations 3 are small, you can carbonization, forms porous carbon.Higher carburizing temperature obtains after can causing carbonization
Carbon it is more regular.
The catalyst that the present invention obtains can be easy to be activated, the method provided according to the present invention, it is preferable that described multiple
Mould assembly hydrogenation catalyst is the catalyst after activation process, and the step of activation process includes：At 25 DEG C~95 DEG C, use is dense
Spend the aqueous slkali for 0.5~30wt% and carry out activation process to the composite hydrogenation catalyst, in Aluminum, zinc and silicon extremely
Few one kind.The aqueous slkali is preferably NaOH or KOH, when the activation process time of aqueous slkali is preferably 5 minutes~72 small.
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 by 100wt% of overall catalyst weight), preferably Raney metal load capacity for 10~
Catalyst after the activation of 80wt%, more preferably Raney metal load capacity are 40~80wt%.
The composite hydrogenation catalyst particle prepared by the method is processed into the size that granularity is 0.1~1mm, it is simultaneous
Care for active metal utilization ratio and easy to separate.
The invention comprehensively utilizes the absorption property of coconut husk charcoal and the hydrogenating reduction ability of hydrogenation catalyst, can efficiently improve
The UV transmittance of ethylene glycol product, the coconut husk charcoal can adsorb part unsaturated compound, trace meter in ethylene glycol
Ion, sulfur-bearing catalyst poison etc., the composite hydrogenation catalyst can will influence the unsaturation of ethylene glycol UV transmittance
Organic matter hydrogenating reduction.
The beneficial effects of the present invention are：The composite hydrogenation catalyst preparation process is simple, catalyst prod impurity
Few, the load capacity of active metal is high, and catalyst granules intensity is good, and activity is high during for hydrofining reaction, can significantly improve
The UV transmittance of ethylene glycol crude product；The invention comprehensively utilizes the absorption property of coconut husk charcoal and adding for composite hydrogenation catalyst
Hydrogen reduction ability, efficiently improves the UV transmittance of ethylene glycol crude product, and processing equipment is simple, investment is small.
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%.
Preparation example 1
The preparation of composite hydrogenation catalyst：
(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) weigh the epoxy resin solidifying system prepared in 50g steps (1) and 150g Nickel Aluminium Alloy Powders be sufficiently stirred it is mixed
Close, Ni contents be 48wt% in nickel alumin(i)um alloy, and aluminium content 52wt%, takes appropriate mixture to be added in cylindrical die, with putting down
Plate vulcameter is molded 30min under conditions of 120 DEG C of temperature, pressure 7MPa, with compression molding instrument in 150 DEG C of temperature, pressure
90min is molded under conditions of 7MPa, cooling is taken out, that is, obtains particulate catalyst precursor；
(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
700 DEG C, when holding 3 is small, nitrogen protection, nitrogen flow 200ml/min, obtains catalyst after nitrogen protection cooling, will urge
Agent crushes, and collects the particle that granular size is 0.1~1mm and is used as catalyst；
(4) 20%NaOH aqueous solution 400g are configured with deionized water, adds the catalyst 50ml obtained by step (3), kept
Temperature 50 C, 1 it is small when after filter out solution, nickel content of metal is about 50wt% in final catalyst, wash to close to neutrality
Afterwards, deposit in spare in deionized water.
Embodiment 1
By ethylene glycol crude product 3kg, coconut husk charcoal 75g, composite hydrogenation catalyst 75g is added between 5L made from preparation example 1
Have a rest in autoclave, it is 90 DEG C, Hydrogen Vapor Pressure 0.4MPa, 100 turns/min of autoclave rotating speed to adjust temperature, processing time 5
Hour.Raw material UV transmittance before hydrogenation：220nm3.2%, product measures ultraviolet printing opacity using ultraviolet specrophotometer after hydrogenation
Rate, is shown in Table 1.
Embodiment 2
By ethylene glycol crude product 3kg, coconut husk charcoal 50g, composite hydrogenation catalyst 100g is added between 5L made from preparation example 1
Have a rest in autoclave, it is 90 DEG C, Hydrogen Vapor Pressure 0.4MPa, 100 turns/min of autoclave rotating speed to adjust temperature, processing time 5
Hour.Raw material UV transmittance before hydrogenation：220nm3.2%, product measures ultraviolet printing opacity using ultraviolet specrophotometer after hydrogenation
Rate, is shown in Table 1.
Embodiment 3
Purifying ethylene glycol experiment is carried out according to the method for embodiment 2, difference is that coconut husk charcoal dosage is 100g, makes
The dosage of composite hydrogenation catalyst made from standby example 1 is 50g, and product is measured ultraviolet using ultraviolet specrophotometer after hydrogenation
Light rate, is shown in Table 1.
Embodiment 4
Purifying ethylene glycol experiment is carried out according to the method for embodiment 2, difference is that coconut husk charcoal dosage is 30g, prepares
The dosage of composite hydrogenation catalyst made from example 1 is 120g, and product is measured ultraviolet using ultraviolet specrophotometer after hydrogenation
Light rate, is shown in Table 1.
Comparative example 1
Purifying ethylene glycol experiment is carried out according to the method for embodiment 1, difference is, is added without coconut husk charcoal, after hydrogenation
Product is shown in Table 1 using ultraviolet specrophotometer measure UV transmittance.
Comparative example 2
Purifying ethylene glycol experiment is carried out according to the method for embodiment 1, difference is, is added without made from preparation example 1
Composite hydrogenation catalyst, product is shown in Table 1 using ultraviolet specrophotometer measure UV transmittance after hydrogenation.
Comparative example 3
Purifying ethylene glycol experiment is carried out according to the method for embodiment 1, difference is, coconut husk charcoal and preparation example 1 are made
Composite hydrogenation catalyst dosage be respectively 1：20, the total dosage of catalyst is 150g, and product uses ultraviolet spectrometry light after hydrogenation
Degree meter measure UV transmittance, is shown in Table 1.
Comparative example 4
Purifying ethylene glycol experiment is carried out according to the method for embodiment 1, difference is, used catalyst is equivalent tradition
Gama-alumina loads 50wt%Ni catalyst, and product is shown in Table 1 using ultraviolet specrophotometer measure UV transmittance after hydrogenation.
The ethylene glycol product 220nm UV transmittances that the different process for purification of table 1 obtain
| Experiment numbers | 220nm UV transmittances (%) |
| Embodiment 1 | 72% |
| Embodiment 2 | 73% |
| Embodiment 3 | 65% |
| Embodiment 4 | 76% |
| Comparative example 1 | 5.2% |
| Comparative example 2 | 0.5% |
| Comparative example 3 | 46% |
| Comparative example 4 | 11% |
It is visible by UV transmittance measurement result：In embodiment 1-5, make jointly in coconut husk charcoal and compound hydrogenation catalyst
Under, it can obtain preferable as a result, ethylene glycol product treatment effeciency is high；In comparative example 1-2,4, exclusive use coconut husk charcoal,
Compound hydrogenation catalyst or the effect of conventional aluminium oxide supported catalyst prepared by the present invention is all very poor, not as using at the same time
It is efficient that coconut husk charcoal and catalyst handle 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 purifying ethylene glycol, it is characterised in that this method comprises the following steps：The contact of composite hydrogenation catalyst, hydrogen, coconut husk charcoal and ethylene glycol crude product is reacted；The coconut husk charcoal with it is described multiple The mass ratio of mould assembly hydrogenation catalyst is 1:10~20:1, the gross mass of the coconut husk charcoal and composite hydrogenation catalyst is second two 1~10wt% of alcohol crude product quality；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 purifying ethylene glycol according to claim 1, wherein, the coconut husk charcoal is catalyzed with the composite hydrogenation The mass ratio of agent is 1:5~10:1, it is preferably 1:2~5:1.
- 3. the method for purifying ethylene glycol according to claim 1, wherein, the coconut husk charcoal and composite hydrogenation catalyst Gross mass is 2~8wt% of ethylene glycol crude product quality, is preferably 3~5wt%.
- 4. the method for purifying ethylene glycol according to claim 1, wherein, it is preferably 5 when the reaction time is 0.5~48 small ~24 it is small when；Reaction temperature is 50 DEG C~120 DEG C, is preferably 80 DEG C~100 DEG C；Hydrogen Vapor Pressure is 0.1~20MPa, is preferably 0.3~2MPa.
- 5. the method for purifying ethylene glycol according to claim 1, wherein, the organic matter being carbonized is organic polymer Compound, the organic high molecular compound include natural organic polymer compounds and synthetic organic polymer compound；Institute It is preferably at least one of starch, viscose rayon, lignin and cellulose to state natural organic polymer compounds；The synthesis Organic high molecular compound is preferably plastics and/or rubber, more preferably epoxy resin, phenolic resin, furane resins, poly- At least one of styrene, styrene-divinylbenzene copolymer, polyacrylonitrile, butadiene-styrene rubber and polyurethane rubber.
- 6. the method for purifying ethylene glycol according to claim 1, wherein, the preparation method of the composite hydrogenation catalyst For：Molded curing and high temperature cabonization are carried out after the organic matter that can be carbonized is mixed with Raney alloy particle.
- 7. the method for purifying ethylene glycol according to claim 6, wherein, Raney alloy particle and the organic matter that can be carbonized Weight ratio is 1:99~99:1, it is preferably 10:90~90:10, more preferably 25:75~75:25.
- 8. the method for purifying ethylene glycol according to claim 1, wherein, Raney alloy particle includes Raney metal and can quilt The weight ratio of the element of leaching, Raney metal and the element that can be leached is 1:99~10:1, it is preferably 1:10~4:1, it is described Raney metal is selected from least one of nickel, cobalt, copper and iron, the element being leached in aluminium, zinc and silicon at least It is a kind of.
- 9. the method for the purifying ethylene glycol according to any one of claim 1-8, wherein, Raney alloy particle further includes rush Into agent, the accelerating agent is selected from least one of Mo, Cr, Ti, Fe, Pt, Pd, Rh and Ru；The amount of the accelerating agent accounts for thunder Buddhist nun 0.01wt%~5wt% of alloy particle total amount.
- 10. the method for the purifying ethylene glycol according to any one of claim 1-8, wherein, the composite hydrogenation catalysis Agent is the catalyst after activation process, and the step of activation process includes：At 25 DEG C~95 DEG C, with concentration for 0.5~ The aqueous slkali of 30wt% carries out activation process to the composite hydrogenation catalyst.
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| 张晓明: "煤基乙二醇变色机理及脱色方法研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
| 陈波: "催化加氢法提高煤制乙二醇UV值的工艺研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115215732A (en) * | 2022-07-11 | 2022-10-21 | 北京算盘工业科技有限公司 | Method and equipment for purifying ethylene glycol |
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