CN107973701B - Method for hydrofining polyester-grade ethylene glycol - Google Patents
Method for hydrofining polyester-grade ethylene glycol Download PDFInfo
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- CN107973701B CN107973701B CN201610939665.8A CN201610939665A CN107973701B CN 107973701 B CN107973701 B CN 107973701B CN 201610939665 A CN201610939665 A CN 201610939665A CN 107973701 B CN107973701 B CN 107973701B
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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
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- 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
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Abstract
The invention provides a method for hydrofining polyester-grade ethylene glycol, which comprises a hydrogenation process and a post-hydrogenation circulation process; in the hydrogenation process, a composite hydrogenation catalyst, hydrogen and a crude ethylene glycol product are contacted to react to obtain a product material flow; in the post-hydrogenation recycle process, returning 40-95% of the product stream to the hydrogenation process; the composite hydrogenation catalyst comprises: continuous phase carbon and dispersed phase Raney alloy particles, wherein the dispersed phase Raney alloy particles are uniformly or non-uniformly dispersed in the continuous phase carbon, and the continuous phase carbon is obtained by carbonizing a carbonizable organic matter or a mixture thereof. After the process is subjected to hydrogenation and quality improvement, polyester-grade ethylene glycol can be obtained; the yield and the quality index of the ethylene glycol product can be adjusted.
Description
Technical Field
The invention relates to the field of hydrofining glycol, and more particularly relates to a method for hydrofining polyester-grade glycol.
Background
Ethylene glycol is an important chemical raw material, has wide application and can be used as an antifreezing agent and a raw material of polyester fibers. Ethylene glycol can be mixed with water at will, has high boiling point and low freezing point, is a very common antifreezing agent, is used as an important organic chemical raw material, and is widely applied to the preparation fields of polyester chips, various antifreezing solutions, coolants, rosin esters, drying agents, softeners and the like.
The ethylene glycol is mainly used for producing polyester and the automobile antifreeze fluid, and the ethylene glycol consumed by the polyester and the automobile antifreeze fluid accounts for more than 90 percent of the total amount, wherein the polyester accounts for 79.5 percent, and the antifreeze fluid accounts for 12.4 percent. When the ethylene glycol is used for producing polyester chips, the requirement on the purity of raw materials is higher, and the national standard is about to be a high-grade product ethylene glycol. In the quality standard of the glycol which is a superior product, an ultraviolet transmittance index (UV value) is provided, and ultraviolet light with the wavelength of 350nm, the wavelength of 275nm and the wavelength of 220nm is respectively measured. The low-content impurities which are not suitable for routine detection in the glycol product have different absorption degrees on the three kinds of wavelength light, so that the ultraviolet light transmittance can accurately reflect the impurity content of the glycol product, and the control value of the index is clearly specified in the national standard.
Due to the different technical routes of ethylene glycol production, the impurity types are also many, but the main substances which influence the UV value of the product and are generally accepted at present are compounds containing carbonyl or conjugated double bonds. The unsaturated compounds have strong absorption at 220nm, so that the ultraviolet transmittance of an ethylene glycol sample at 220nm can represent the purity of ethylene glycol to a certain extent.
In order to improve the quality of ethylene glycol products, methods for improving the purity of ethylene glycol are continuously developed, and the current process technologies for purifying ethylene glycol are mainly divided into an adsorption method and a deep hydrogenation method.
The adsorption method is widely implemented in recent years, and is characterized by simple process and low investment, and the impurities in the ethylene glycol are removed by utilizing the selective adsorption of an adsorbent, so that the UV value of the product is improved. The PPG company in 1976 noted that Activated Carbon (AC) was able to adsorb unsaturated compounds in ethylene glycol, significantly increasing the UV transmittance of ethylene glycol. WO9958483 and US 391711 respectively describe a process for purifying organic liquids, in particular alcohols, with activated carbon, which increases the UV transmittance of the alcohol without significantly increasing its pH. However, it has been found that the selectivity of adsorption of unsaturated compounds is not high, since the material carbon is not active enough and difficult to modify. The research on the influence of NY type homogeneous catalysts on the UV value of ethylene glycol products is conducted by Zhang bin of Nanjing industry university, and the research finds that the produced ethylene glycol can reach the advanced chemical fiber grade standard of American SD company under certain process conditions. Because the ion exchange resin is an adsorption material with adjustable surface functional groups, the selective adsorption of impurities can be realized by utilizing the adjustment of surface anions and cations. U.S. Pat. No. 5,6187973 reports the use of anion exchange data, which have been exchanged with sulfite to provide a strong base anion exchange resin, which is primarily directed to the removal of aldehydes and also to the enhancement of the UV transmittance of ethylene glycol. The existing dealdehyding resin manufacturers in China are mainly Jiangsu Suqing water treatment companies and Kery chemical industry, and carry out selective adsorption on unsaturated compounds in crude glycol through the adsorption effect of ion exchange resin, so that the UV value of the product is improved. Although the adsorption method can improve the UV value of the product, the total adsorption amount and the single-pass adsorption capacity of the adsorbent are limited, so that the improvement degree of the UV value of the glycol product is low, the controllable range is narrow, and the capacity for treating the glycol product with the low UV value is insufficient.
US4289593 describes a method of irradiating technical grade ethylene glycol to fibre grade standards using a uv light source. The wavelength of light used for irradiation is at least 220nm, preferably higher than 240nm, and the transmittance of ethylene glycol is significantly improved at wave numbers of 220nm, 275nm and 350nm after irradiation.
US43494171 reports a method for increasing the UV value of ethylene glycol by adding a base. The glycol prepared by the method has high purity, the ultraviolet light transmittance at 220nm is higher than 70%, and the added alkali metal compound does not influence the refining equipment of a post system. Another additive reported in U.S. Pat. No. 4,4358625 is an alkali metal borohydride, which is added before or after the ethylene oxide is mixed with water, the most common being the addition of NaBH4The added solution can be solid or stable solution; the UV value of the glycol product produced by processing the raw materials is effectively improved, and the level of polyester grade is achieved. Patent document US5440058 teaches active, generally relatively volatile organic or inorganic compounds which, when formed as by-products, can be removed again by converting them into less volatile substancesIf the conversion into salt is carried out, the salt can be removed by means of distillation, extraction, membrane separation or a solid bed; they used the addition of sodium bisulfite to remove carbon-based impurities such as aldehydes and ketones. European patent document EP310189 describes a process for purifying ethylene glycol by the dicumyl oxalate process. The ethylene glycol is distilled at a PH of 7.5 to remove impurities that affect the uv transmittance of the ethylene glycol to fiber grade standards.
In a word, the ethylene glycol product contains trace amount of unsaturated compounds such as carboxylic acid, aldehyde, conjugated olefine aldehyde and the like, so that the ultraviolet transmittance of the product in the range of 220-350nm is low, and the quality of downstream product polyester is influenced. In order to improve the ultraviolet transmittance of ethylene glycol, a certain method is required to remove trace unsaturated substances, so that the ultraviolet transmittance of ethylene glycol products is improved.
In industrial production, polyester grade glycol is the main use of ethylene glycol, and the requirement of the polyester grade glycol on product purity is high, so that the polyester grade glycol needs to reach a high-quality product. However, in the petrochemical route, the product quality is unstable due to various conditions, even some glycol products are good in appearance, but the ultraviolet transmittance (220nm) of the glycol products is between 1.0 and 5.0 percent, and the index of the polyester grade glycol is required to be more than 75 percent or even higher.
Disclosure of Invention
The invention aims to provide a method for hydrorefining polyester-grade ethylene glycol aiming at the problem of unstable product quality caused by various conditions in the prior ethylene glycol production technology, and the polyester-grade ethylene glycol can be obtained after hydrogenation and quality improvement; the yield and the quality index of the ethylene glycol product can be adjusted.
In order to achieve the above object, the present invention provides a process for hydrorefining polyester grade ethylene glycol, comprising a hydrogenation process and a post-hydrogenation recycle process;
in the hydrogenation process, a composite hydrogenation catalyst, hydrogen and a crude ethylene glycol product are contacted to react to obtain a product material flow; in the post-hydrogenation recycle process, returning 40-95% of the product stream to the hydrogenation process;
the composite hydrogenation catalyst comprises: continuous phase carbon and dispersed phase Raney alloy particles, wherein the dispersed phase Raney alloy particles are uniformly or non-uniformly dispersed in the continuous phase carbon, and the continuous phase carbon is obtained by carbonizing a carbonizable organic matter or a mixture thereof.
The product material obtained after the hydrogenation reaction in the hydrogenation process is qualified, and the product material is returned to the hydrogenation process, namely, one part of the product material obtained after the reaction in the hydrogenation reactor is returned to the hydrogenation reactor, and is mixed with fresh non-hydrogenated reaction raw materials and then enters the hydrogenation reactor. The purpose of the returning process is to dilute the reaction raw materials, reduce the content of impurities affecting the quality of the ethylene glycol in the reaction raw materials, and after the operation is stable, the hydrofined ethylene glycol product can more easily meet the requirement of polyester grade.
According to the method provided by the present invention, preferably, the conditions of the hydrogenation process include: the reaction temperature is 50-200 ℃, the reaction pressure is 0.1-8.0 MPa, and the reaction space velocity measured by the liquid volume of the crude ethylene glycol is 0.05-20 h-1The volume ratio of the hydrogen to the ethylene glycol crude product is 200-10000: 1; the preferable reaction temperature is 80-120 ℃, the reaction pressure is 0.2-2.0 MPa, and the reaction space velocity measured by the liquid volume of the crude ethylene glycol is 0.1-6.0 h-1The volume ratio of the hydrogen to the ethylene glycol crude product is 600-2000: 1.
According to the method provided by the invention, preferably, in the post-hydrogenation recycling process, 80-95% of the first stream is returned to the hydrogenation process.
According to the method provided by the invention, the organic matter capable of being carbonized refers to: treating organic matter at certain temperature and atmosphere condition to volatilize most or all of hydrogen, oxygen, nitrogen, sulfur and other components in the organic matter, so as to obtain one kind of synthetic material with high carbon content.
The organic matter capable of being carbonized is at least one selected from organic high molecular compounds, coal, natural asphalt, petroleum asphalt and coal tar asphalt. Preferably, the organic matter capable of being carbonized is an organic polymer compound including a natural organic polymer compound and a synthetic organic polymer compound; the natural organic high molecular compound is preferably at least one of starch, viscose, lignin and cellulose; the synthetic organic polymer compound is preferably plastic and/or rubber, and is further preferably at least one of epoxy resin, phenolic resin, furan resin, polystyrene, styrene-divinylbenzene copolymer, polyacrylonitrile, styrene-butadiene rubber and polyurethane rubber.
According to the method provided by the present invention, preferably, the raney alloy particles comprise raney metal and an element that can be leached. "Raney metal" means a metal that is insoluble when activated by Raney process, said Raney metal being selected from at least one of nickel, cobalt, copper and iron. "leachable element" means an element that is soluble when activated by raney and is selected from at least one of aluminum, zinc, and silicon. The Raney alloy particles are selected from nickel-aluminum alloy, cobalt-aluminum alloy or copper-aluminum alloy, preferably nickel-aluminum alloy. In the raney alloy particles, the weight ratio of raney metal to leachable elements is 1: 99-10: 1, preferably in the range of 1: 10-4: 1. the average particle diameter of the Raney alloy particles is generally 0.1-1000 microns, preferably 10-100 microns.
According to the method provided by the invention, in order to improve the activity or selectivity of the catalyst, the Raney alloy particles further comprise a promoter, and the amount of the promoter accounts for 0.01-5 wt% of the total amount of the Raney alloy particles; the promoter is at least one selected from Mo, Cr, Ti, Fe, Pt, Pd, Rh and Ru.
According to the method provided by the invention, preferably, the preparation method of the composite hydrogenation catalyst comprises the following steps: and mixing the organic matter capable of being carbonized with the Raney alloy particles, and then carrying out die pressing solidification and high-temperature carbonization to obtain the composite of continuous phase carbon and the Raney alloy particles.
Further preferably, the preparation method of the composite catalyst comprises the following steps:
a. mixing a carbonizable organic substance with an additive to prepare a curing system;
b. uniformly mixing the Raney alloy particles with the curing system, and then carrying out mould pressing and curing to obtain a catalyst precursor;
c. carbonizing the catalyst precursor at 400-1900 ℃ under the protection of inert gas;
in step a, the curing system is formulated according to a conventional curing formulation for organic carbonizable compounds, said additives being selected from at least one of curing accelerators, dyes, pigments, colorants, antioxidants, stabilizers, plasticizers, lubricants, flow modifiers or adjuvants, flame retardants, anti-drip agents, anti-blocking agents, adhesion promoters, electrical conductivity agents, polyvalent metal ions, impact modifiers, mold release aids and nucleating agents. The dosage of the used additives is conventional dosage or is adjusted according to the requirements of actual conditions. The prepared solidification system is a liquid system or a powder system, and the liquid system can be directly stirred uniformly; the powder system can be directly and uniformly blended; the powder system can be pulverized by any pulverizing equipment commonly used in industry and then uniformly blended.
In step b, the weight ratio of the raney alloy particles to the carbonizable organic substance is 1: 99-99: 1, preferably 10: 90-90: 10, more preferably 25: 75-75: 25. the obtained catalyst precursor can be processed into particles which can be used in a fixed bed or a fluidized bed reaction by cutting, stamping or crushing and the like by any available organic polymer material processing equipment, wherein the particle size of the particles is based on the particle size which can meet the requirements of a fixed bed catalyst or a fluidized bed catalyst, and the shape of the particles can be selected from any irregular shape, spheroid, hemispheroid, cylinder, hemicylinder, prism, cube, cuboid, ring, hemiring, hollow cylinder, tooth shape or the combination of the shapes, and the like, and at least one of sphere, ring, tooth shape and cylinder shape is preferred.
In step c, the carbonization is generally performed in a tubular heating furnace, the carbonization operation temperature is generally 400-1900 ℃, preferably 600-950 ℃, the protective gas is inert gas such as nitrogen or argon, and the carbonization time is 1-12 hours. For example, phenolic resin is carbonized at 850 ℃ for 3 hours, and then the phenolic resin is completely carbonized to form porous carbon. The higher carbonization temperature can make the carbon obtained after carbonization more regular.
According to the method provided by the invention, preferably, the composite hydrogenation catalyst is a catalyst after activation treatment, and the activation treatment step comprises: activating the composite hydrogenation catalyst by using an alkali solution with the concentration of 0.5-30 wt% at the temperature of 25-95 ℃; further preferably, the alkali solution is NaOH or KOH, and the activation treatment time is 5 minutes to 72 hours.
The loading of the raney metal in the catalyst can be easily controlled by controlling the addition amount of the raney alloy particles and/or controlling the activation degree of the catalyst during the preparation process of the catalyst, for example, an activated catalyst with a raney metal loading of 1 to 90 wt% (based on 100% of the total weight of the catalyst), preferably an activated catalyst with a raney metal loading of 10 to 80 wt%, and more preferably 40 to 80 wt% can be obtained.
According to the invention, a carbonizable organic substance and the Raney alloy particles are mixed and then carbonized to obtain a composite of carbon and the Raney alloy particles, the Raney alloy particles play a role in promoting the carbonization process and can ensure that the carbonization is more complete, after the carbonization, the Raney alloy particles are dispersed in a continuous phase of the carbon and firmly combined with the continuous phase carbon, and the continuous phase carbon has a porous structure, so that the obtained catalyst has very high strength. Meanwhile, the particles of the Raney alloy are distributed in the gaps of the carbon, the solution or the gas can easily contact the Raney alloy, the composite catalyst is soaked by the alkali liquor, the particles of the Raney alloy are activated to form porous high-activity Raney metal, a small amount of amorphous carbon is washed away, the continuous phase carbon material is expanded, more particles of the Raney alloy are exposed, and therefore the catalyst has high activity.
The invention has the beneficial effects that: the catalyst product used in the method has less impurities, high loading amount of active metal and good strength of catalyst particles, and has high activity when being used for hydrofining reaction; the high-activity composite hydrofining catalyst is combined with the product circulation process after hydrogenation, so that the ultraviolet transmittance of the glycol can be obviously improved, and the glycol can meet the quality requirement of polyester-grade glycol.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below with reference to examples. While the preferred embodiments of the present invention have been described in the examples, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein.
According to lambert-beer's law, the absorbance (a) is proportional to the product of the solution layer thickness (b) and the concentration (c), i.e., a ═ kbc, a ═ lgT. The absorption coefficient of a substance does not change at the same wavelength. In addition, as can be seen from the ultraviolet spectrum principle, pure ethylene glycol does not absorb at a wavelength of 200nm or more, so the concentration c can be approximated to the total concentration of such impurities, and the impurity removal rate is obtained from lgT in a linear relationship with the total concentration c of impurities:
note: x: the impurity removal rate; c. C0: the impurity concentration of the feedstock; c. C1: the impurity concentration after hydrogenation; t is0: ultraviolet transmittance of the raw material; t is1: ultraviolet transmittance after hydrogenation.
The requirements of the national standard for industrial ethylene glycol (GB/T4649-2008) on the ultraviolet transmittance of a high-quality ethylene glycol product are as follows:
220nm is more than or equal to 75 percent
275nm greater than or equal to 92%
99% or more of 350 nm.
The ultraviolet transmittance indexes of the glycol raw material to be hydrofined are as follows: 0.5-5% of 220nm, 20-70% of 275nm, 40-99% of 350nm, and transparent and colorless appearance.
Preparation example
Preparing a composite hydrogenation catalyst CAT-1:
(1) uniformly stirring 100 parts by mass of liquid epoxy resin (ba ling petrochemical, CYD-128), 85 parts by mass of curing agent methyl tetrahydrophthalic anhydride (MeTHPA) (Kyoto Kodao Co., Ltd., Guangdong Shengshida) and 1.5 parts by mass of curing accelerator Triethanolamine (TEA) (chemical reagent factory, Tianjin city);
(2) weighing 40g of the epoxy curing system prepared in the step (1) and 180g of nickel-aluminum alloy powder, fully stirring and mixing, wherein the Ni content in the nickel-aluminum alloy is 48 wt% and the aluminum content is 52 wt%, adding a proper amount of the mixture into a cylindrical mold, molding for 30mins at the temperature of 120 ℃ and the pressure of 7MPa by using a flat-plate vulcanizing instrument, molding for 90mins at the temperature of 150 ℃ and the pressure of 7MPa by using a flat-plate vulcanizing instrument, cooling and taking out to obtain a granular catalyst precursor;
(3) measuring 100ml of catalyst precursor, putting the catalyst precursor into a tubular high-temperature electric furnace, keeping the temperature at the rate of 10 ℃/min and the carbonization temperature of 600 ℃ for 3 hours under the protection of nitrogen, wherein the nitrogen flow is 200ml/min, and cooling under the protection of nitrogen to obtain the catalyst;
(4) preparing 400g of 20% NaOH aqueous solution by using deionized water, adding 50ml of the catalyst obtained in the step (3), keeping the temperature at 85 ℃, filtering the solution after 4 hours to obtain the activated composite catalyst, and finally storing the catalyst in the deionized water after the nickel metal loading amount in the catalyst is about 60 wt% and the catalyst is washed to be nearly neutral.
Example 1
Hydrofining ethylene glycol liquid through a fixed bed reactor, loading a compound hydrogenation catalyst CAT-150ml into the fixed bed reactor, wherein the inner diameter of a pipe is 25mm, the hydrogen flow is 200ml/min, the reaction temperature is 100 ℃, the pressure is 0.5MPa, and the empty speed of the ethylene glycol liquid is 6.0h-1(ii) a Ultraviolet transmittance of raw materials before hydrogenation: 220nm 2.6%, 275nm 50% and 350nm 76%, the product return ratio after hydrogenation is 95%, and the ultraviolet transmittance of the product after hydrogenation is measured by using an ultraviolet spectrophotometer and is shown in table 1.
Example 2
Glycol was hydrorefined according to the method of example 1, except that the product return ratio after hydrogenation was 90%; ultraviolet transmittance of raw materials before hydrogenation: 220nm 2.6%, 275nm 50% and 350nm 76%, and the ultraviolet transmittance of the hydrogenated product is measured by using an ultraviolet spectrophotometer and is shown in table 1.
Example 3
Glycol was hydrorefined according to the method of example 1, except that the product return ratio after hydrogenation was 80%; ultraviolet transmittance of raw materials before hydrogenation: 220nm 2.6%, 275nm 50% and 350nm 76%, and the ultraviolet transmittance of the hydrogenated product is measured by using an ultraviolet spectrophotometer and is shown in table 1.
Example 4
Glycol was hydrorefined according to the method of example 1, except that the product return ratio after hydrogenation was 40%; ultraviolet transmittance of raw materials before hydrogenation: 220nm 2.6%, 275nm 50% and 350nm 76%, and the ultraviolet transmittance of the hydrogenated product is measured by using an ultraviolet spectrophotometer and is shown in table 1.
Example 5
Ethylene glycol was hydrorefined according to the method of example 3, except that the amount of CAT-1 as the composite hydrogenation catalyst was 100 ml; the product after hydrogenation was measured for ultraviolet transmittance using an ultraviolet spectrophotometer and is shown in table 1.
Example 6
Ethylene glycol was hydrorefined according to the method of example 3, except that the amount of CAT-1 as the composite hydrogenation catalyst was 200 ml; the product after hydrogenation was measured for ultraviolet transmittance using an ultraviolet spectrophotometer and is shown in table 1.
Comparative example 1
Ethylene glycol was hydrofinished according to the method of example 1, except that the product was not returned after hydrogenation; ultraviolet transmittance of raw materials before hydrogenation: 220nm 2.6%, 275nm 50% and 350nm 76%, and the ultraviolet transmittance of the hydrogenated product is measured by using an ultraviolet spectrophotometer and is shown in table 1.
Comparative example 2
Ethylene glycol was hydrorefined according to the method of example 3, except that the product was not returned after hydrogenation, and the space velocity of the reaction feed, ethylene glycol liquid, was from 6.0h-1The reduction is 1.2h-1(ii) a Ultraviolet transmittance of raw materials before hydrogenation: 220nm 2.6%, 275nm 50% and 350nm 76%, and the ultraviolet transmittance of the hydrogenated product is measured by using an ultraviolet spectrophotometer and is shown in table 1.
Comparative example 3
Ethylene glycol was hydrofinished according to the method of example 1, except that the catalyst used in the hydrofinishing process was an alumina-supported nickel metal catalyst, which was used in the same amount as in example 1. Nickel metal catalyst supported on aluminaPreparing by an overpressure sheet method: 1kg of basic nickel carbonate NiCO3·2Ni(OH)2·4H2Mixing and kneading O and a certain amount of pseudo-boehmite, drying, roasting, granulating, tabletting and forming into cylindrical catalyst particles with the diameter of phi 3mm multiplied by 3mm, wherein the reduced catalyst contains 56 wt% of nickel metal and is used for fixed bed hydrogenation reaction. The product after hydrogenation was measured for ultraviolet transmittance using an ultraviolet spectrophotometer and is shown in table 1.
TABLE 1 UV transmittance of ethylene glycol products obtained by different methods
And (4) experimental conclusion: the results of the embodiment show that the higher the product return ratio after hydrogenation is, the better the hydrofining effect is, and the hydrogenation process can effectively hydrofine the glycol into glycol products with higher purity, even polyester grade glycol products; compared with the comparative examples 1-2 without the return step and the comparative example 3 without the composite hydrogenation catalyst prepared by the invention, the hydrogenation process adopted by the invention has better effect of refining and purifying the glycol product.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.
Claims (14)
1. A method for hydrofining polyester-grade ethylene glycol is characterized by comprising a hydrogenation process and a post-hydrogenation recycling process;
in the hydrogenation process, a composite hydrogenation catalyst, hydrogen and a crude ethylene glycol product are contacted to react to obtain a product material flow; in the post-hydrogenation recycle process, returning 80-95% of the product stream to the hydrogenation process;
the composite hydrogenation catalyst comprises: continuous phase carbon and dispersed phase Raney alloy particles, wherein the dispersed phase Raney alloy particles are uniformly or non-uniformly dispersed in the continuous phase carbon, and the continuous phase carbon is obtained by carbonizing a carbonizable organic matter or a mixture thereof;
the conditions of the hydrogenation process include: the reaction temperature is 50-200 ℃, the reaction pressure is 0.1-8.0 MPa, and the reaction space velocity measured by the liquid volume of the crude ethylene glycol is 0.05-20 h-1The volume ratio of the hydrogen to the ethylene glycol crude product is 200-10000: 1;
the raney alloy particles comprise raney metal and a leachable element in a weight ratio of 1: 99-10: 1, the raney metal is selected from at least one of nickel, cobalt, copper and iron, and the leachable element is selected from at least one of aluminum, zinc and silicon.
2. The process for hydrofinishing polyester grade ethylene glycol according to claim 1, wherein,
the reaction temperature is 80-120 ℃, the reaction pressure is 0.2-2.0 MPa, and the reaction space velocity measured by the liquid volume of the crude ethylene glycol is 0.1-6.0 h-1The volume ratio of the hydrogen to the ethylene glycol crude product is 600-2000: 1.
3. The process for hydrofinishing polyester grade ethylene glycol according to claim 1, wherein,
the organic matter capable of being carbonized is an organic high molecular compound, and the organic high molecular compound comprises a natural organic high molecular compound and a synthetic organic high molecular compound.
4. The process for hydrofinishing polyester grade ethylene glycol according to claim 3, wherein,
the natural organic high molecular compound is at least one of starch, viscose, lignin and cellulose.
5. The process for hydrofinishing polyester grade ethylene glycol according to claim 3, wherein,
the synthetic organic high molecular compound is plastic and/or rubber.
6. The process for hydrofinishing polyester grade ethylene glycol according to claim 5, wherein,
the synthetic organic high molecular compound is at least one of epoxy resin, phenolic resin, furan resin, polystyrene, styrene-divinylbenzene copolymer, polyacrylonitrile, styrene-butadiene rubber and polyurethane rubber.
7. The process for hydrofinishing polyester grade ethylene glycol according to claim 1, wherein,
the preparation method of the compound hydrogenation catalyst comprises the following steps: and mixing the organic matter capable of being carbonized with the Raney alloy particles, and then carrying out die pressing solidification and high-temperature carbonization to obtain the composite of continuous phase carbon and the Raney alloy particles.
8. The process for hydrofinishing polyester grade ethylene glycol according to claim 7, wherein,
the preparation method of the composite catalyst comprises the following steps:
a. mixing a carbonizable organic substance with an additive to prepare a curing system;
b. uniformly mixing the Raney alloy particles with the curing system, and then carrying out mould pressing and curing to obtain a catalyst precursor;
c. carbonizing the catalyst precursor at 400-1900 ℃ under the protection of inert gas;
the additive is selected from at least one of a curing accelerator, a dye, a pigment, a colorant, an antioxidant, a stabilizer, a plasticizer, a lubricant, a flame retardant, an anti-dripping agent, an anti-blocking agent, an adhesion promoter, a conductive agent, a polyvalent metal ion, an impact modifier, a mold release aid, and a nucleating agent.
9. The process for hydrofinishing polyester grade ethylene glycol according to claim 7, wherein,
the weight ratio of the raney alloy particles to the carbonizable organic substance is 1: 99-99: 1.
10. the process for hydrofinishing polyester grade ethylene glycol according to claim 9, wherein,
the weight ratio of the raney alloy particles to the carbonizable organic substance is 10: 90-90: 10.
11. the process for hydrofinishing polyester grade ethylene glycol according to claim 10, wherein,
the weight ratio of the raney alloy particles to the carbonizable organic substance is 25: 75-75: 25.
12. the process for hydrofinishing polyester grade ethylene glycol according to claim 1, wherein,
the weight ratio of raney metal to leachable elements is 1: 10-4: 1.
13. the process for hydrofinishing polyester grade ethylene glycol according to any one of claims 1 to 12, wherein the raney alloy particles further comprise a promoter in an amount of 0.01 to 5 wt% of the total amount of raney alloy particles; the promoter is at least one selected from Mo, Cr, Ti, Fe, Pt, Pd, Rh and Ru.
14. The process for hydrofinishing polyester grade ethylene glycol according to any one of claims 1 to 12, wherein the hybrid hydrogenation catalyst is a post-activation treated catalyst, the step of activation treatment comprising: and activating the composite hydrogenation catalyst by using an alkali solution with the concentration of 0.5-30 wt% at the temperature of 25-95 ℃.
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| 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 |
| CN112174780B (en) * | 2020-09-27 | 2021-07-20 | 于广臣 | Control method for improving UV value of ethylene glycol product through low-pressure catalytic hydrogenation |
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| US5536694A (en) * | 1993-10-16 | 1996-07-16 | Degussa Aktiengesellschaft | Catalyst precursor for an activated raney metal fixed-bed catalyst, an activated raney metal fixed-bed catalyst and a process for its preparation and use, and a method of hydrogenating organic compounds using said catalyst |
| CN104945227A (en) * | 2014-03-27 | 2015-09-30 | 中国石油化工股份有限公司 | Ethylene glycol hydrofining method |
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| US5536694A (en) * | 1993-10-16 | 1996-07-16 | Degussa Aktiengesellschaft | Catalyst precursor for an activated raney metal fixed-bed catalyst, an activated raney metal fixed-bed catalyst and a process for its preparation and use, and a method of hydrogenating organic compounds using said catalyst |
| CN104945227A (en) * | 2014-03-27 | 2015-09-30 | 中国石油化工股份有限公司 | Ethylene glycol hydrofining method |
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