CN107973700B - Method for hydrofining ethylene glycol - Google Patents

Method for hydrofining ethylene glycol Download PDF

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Publication number
CN107973700B
CN107973700B CN201610935675.4A CN201610935675A CN107973700B CN 107973700 B CN107973700 B CN 107973700B CN 201610935675 A CN201610935675 A CN 201610935675A CN 107973700 B CN107973700 B CN 107973700B
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ethylene glycol
hydrogenation
raney
catalyst
alloy particles
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CN107973700A (en
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蒋海斌
鲁树亮
张晓红
吴佳佳
王秀玲
彭晖
乔金樑
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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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
    • 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
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of chromium, molybdenum or tungsten
    • 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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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

The invention provides a method for hydrofining ethylene glycol, which comprises the following steps: in a first reactor, a raney nickel catalyst loaded by a high molecular material, a glycol crude product and hydrogen are contacted for reaction to obtain a first material flow; second-stage hydrogenation: in a second reactor, a first hydrogenation catalyst is contacted with the first material flow and hydrogen to react, so as to obtain a second material flow; optionally, the method further comprises at least one stage of hydrogenation after the second stage of hydrogenation process, and each stage of hydrogenation adopts a composite type hydrogenation catalyst. By the method, poor ethylene glycol raw materials (low ultraviolet transmittance) are subjected to hydrogenation upgrading through a multistage hydrogenation process to obtain the polyester-grade ethylene glycol.

Description

Method for hydrofining ethylene glycol
Technical Field
The invention relates to the technical field of ethylene glycol refining processes, and particularly relates to a method for hydrofining ethylene 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 a high boiling point and a low freezing point, and is a very common antifreezing agent. As an important organic chemical raw material, ethylene glycol is widely applied to the preparation fields of polyester chips, various antifreeze 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 the 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. US6187973 reports the use of anion exchange data for treatment, which have been selected for strong base anion exchange resins exchanged with sulfite for the primary purpose of removing aldehydes while also achieving improved 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 NaBH4(ii) a The 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 compoundsWhen they are formed as by-products, they can be removed again by converting them into less volatile substances; if the conversion into salt can be removed by means of distillation, extraction, membrane separation or 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 distilling ethylene glycol at PH 7.5 using a dicresyl oxalic acid process to remove impurities that affect the uv transmittance of 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 solve the problem of unstable quality of ethylene glycol products, and provides a method for hydrofining ethylene glycol, wherein poor ethylene glycol raw materials (low ultraviolet transmittance) are subjected to hydrogenation and quality improvement through a multistage hydrogenation process to obtain polyester-grade ethylene glycol.
In order to achieve the above object, the present invention provides a method for hydrorefining ethylene glycol, comprising:
first-stage hydrogenation: in a first reactor, a raney nickel catalyst loaded by a high molecular material, a glycol crude product and hydrogen are contacted for reaction to obtain a first material flow,
second-stage hydrogenation: in a second reactor, contacting a composite hydrogenation catalyst with the first material flow and hydrogen to react to obtain a second material flow;
optionally, the method further comprises performing at least one stage of hydrogenation after the second stage of hydrogenation, wherein each stage of hydrogenation adopts a composite hydrogenation catalyst;
the polymer material-supported Raney nickel catalyst comprises: the carrier comprises an organic polymer material used as a carrier and Raney alloy particles loaded on the surface of the organic polymer material, wherein the Raney alloy particles are loaded on the surface of the carrier in a form of being partially embedded into the organic polymer material;
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.
According to the method provided by the invention, preferably, the reaction conditions of each stage of hydrogenation are as follows: the reaction temperature is 50-200 ℃, the reaction pressure is 0.1-8.0MPa, and the reaction space velocity measured by the liquid volume of the ethylene glycol is 0.05-20h-1(ii) a The preferable reaction temperature is 80-120 ℃, the reaction pressure is 0.2-2.0MPa, and the reaction space velocity measured by the liquid volume of the ethylene glycol is 0.1-6h-1(ii) a The pressure required for the reaction is maintained by the hydrogen flow.
According to the process of the present invention, two, three or more stages of hydrogenation may be employed, or it is understood that the second stage of hydrogenation is followed by one or more stages of hydrogenation similar to the second stage of hydrogenation. When the tertiary hydrogenation is carried out, the step of the tertiary hydrogenation comprises: and in a third reactor, contacting the composite hydrogenation catalyst with the second material flow and hydrogen to react to obtain a third material flow. When more stages of hydrogenation are carried out, the hydrotreatment can be carried out sequentially in the reactors in series, as described above.
When three or more stages of hydrogenation are carried out, the amount of the composite hydrogenation catalyst used in each stage of hydrogenation may be the same as that used in the second stage of hydrogenation.
According to the method provided by the invention, preferably, when two-stage hydrogenation is carried out, the weight ratio of the high polymer material-supported raney nickel catalyst to the composite hydrogenation catalyst is 1: 0.1-2.
Preferably, when the three-stage hydrogenation is carried out, the weight of the high molecular material supported raney nickel catalyst used in the first stage hydrogenation is: the weight of the composite hydrogenation catalyst used in the second-stage hydrogenation is as follows: the weight ratio of the composite hydrogenation catalyst used in the third-stage hydrogenation is 1: 0.1-2: 0.1-2.
According to the method provided by the invention, in the polymer material loaded Raney nickel catalyst, the Raney alloy particles preferably contain nickel, iron, chromium, lanthanum and aluminum, and the Raney alloy particles comprise the following components in percentage by weight: 30-60wt% of nickel, 0.01-5wt% of iron, 0.01-5wt% of chromium, 0.01-5wt% of lanthanum and 30-60wt% of aluminum.
Preferably, the organic polymer material is selected from plastics or modified products thereof, preferably at least one of polyolefin, poly 4-methyl-1-pentene, polyamide resin, polycarbonate resin, homo-polyformaldehyde, co-polyformaldehyde, linear polyester prepared by condensation polymerization of saturated dibasic acid and dihydric alcohol, aromatic ring polymer, heterocyclic ring polymer, fluoropolymer, acrylic resin, urethane, epoxy resin, phenolic resin, urea resin and melamine resin; more preferably at least one of polyolefin, polyamide resin, epoxy resin and phenol resin, and further preferably at least one of polypropylene, nylon-6, nylon-66, polystyrene, phenol resin and epoxy resin.
The plastic modified product refers to a modified product obtained by adopting the existing plastic modification method. Plastic modification methods include, but are not limited to, the following: graft modification of polar or non-polar monomers or polymers thereof; the material is modified by melt blending with inorganic or organic reinforcing materials, toughening materials, stiffening materials, heat resistance increasing materials and the like.
According to the method provided by the present invention, preferably, the preparation method of the polymer material supported raney nickel catalyst is as follows: and under the condition of the forming processing temperature of the organic polymer material or the uncured shaping condition, the organic polymer material coated by the Raney alloy particles is molded.
The specific preparation method is slightly different for different organic polymer materials as carriers.
When the carrier is made of thermoplastic organic polymer material, the carrier can be prepared by the following method (i) or (ii):
method (i):
(1) processing a thermoplastic organic high molecular material carrier into particles with the size required by a fixed bed catalyst or a fluidized bed catalyst;
(2) placing the particles of the carrier in the Raney alloy particles, namely the carrier particles are completely coated by the Raney alloy particles;
(3) and under the condition of the forming processing temperature of the thermoplastic organic high polymer material carrier, carrying out die pressing on the carrier placed in the Raney alloy particles, partially pressing the Raney alloy particles into the carrier particles, loading the Raney alloy particles on the surfaces of the carrier particles and partially embedding the Raney alloy particles into the carrier, cooling and sieving to obtain the granular catalyst.
The particle size of the obtained granular catalyst is based on the particle size which can satisfy the requirement of a fixed bed catalyst or a fluidized bed catalyst. The shape of the particles may be any irregular shape, spheroid, hemispheroid, cylinder, hemicylinder, prism, cube, cuboid, ring, hemiring, hollow cylinder, and at least one of a tooth, preferably a sphere, a ring, a tooth, and a cylinder. The carrier particles may be shaped from powder or may be used as they are, for example, commercially available shaped carrier particles.
Or method (ii):
(1) processing a thermoplastic organic high molecular material carrier into a sheet with a thickness required by a fixed bed catalyst or a fluidized bed catalyst;
(2) uniformly coating the surface of the sheet with Raney alloy particles;
(3) and (2) under the common molding processing temperature condition of the carrier, carrying out die pressing on the sheet coated with the Raney alloy particles, pressing part of the Raney alloy particles into the sheet serving as the carrier, cooling, processing the sheet with the Raney alloy particles loaded on the surface into particles with required shape and size by using any available processing equipment through methods such as cutting, stamping or crushing, and finally obtaining the granular catalyst.
The support described in process (i) or process (ii) may be provided with auxiliaries which are customary in plastics processing. The auxiliary agent is selected from at least one of an antioxidant, a secondary antioxidant, a heat stabilizer, a light stabilizer, an ozone stabilizer, a processing aid, a plasticizer, a softener, an anti-blocking agent, a foaming agent, a dye, a pigment, a wax, an extender, an organic acid, a flame retardant and a coupling agent. The dosage of the auxiliary agent is conventional dosage or adjusted according to the requirement of actual situation.
When the carrier is a thermosetting organic polymer material, the carrier can be prepared by the following method (iii) or (iv):
method (iii):
(1) preparing a proper curing system according to a common curing formula of the thermosetting organic high polymer material; when the solidification system is a liquid system, the mixture can be directly and uniformly stirred, and when the solidification system is a powder solid system, the mixture can be directly and uniformly mixed; the powdery solid system can be pulverized by any pulverizing equipment commonly used in industry and then uniformly blended.
(2) Adding Raney alloy particles into a die which can meet the particle size required by a fixed bed catalyst or a fluidized bed catalyst, adding the curing system, carrying out partial curing and shaping under the common curing condition, then continuously carrying out mould pressing and curing by any available organic high polymer material processing equipment, and sieving after complete curing to obtain the granular catalyst.
Or method (iv):
(1) preparing a curing system and a liquid system according to a common curing formula of the thermosetting organic high polymer material; when the solidification system is a liquid system, the mixture can be directly and uniformly stirred, and when the solidification system is a powder solid system, the mixture can be directly and uniformly mixed; the powdery solid system can be crushed by any crushing equipment commonly used in industry and then is blended uniformly;
(2) under the common curing condition, the curing system is molded into a sheet by any available equipment, the sheet is not completely cured, the thickness is determined by the size of a fixed bed catalyst or a fluidized bed catalyst, the upper surface and the lower surface of the sheet are uniformly coated with Raney alloy particles, then the sheet is continuously molded to be completely cured, the Raney alloy particles are partially pressed into a carrier, and the surface of the sheet serving as the carrier is loaded by the Raney alloy particles, so that the catalyst is obtained;
(3) the prepared catalyst is processed into particles which can be used in a fixed bed or a fluidized bed reaction by adopting any available organic polymer material processing equipment through methods of cutting, stamping or crushing, and the like, wherein the particle size of the particles is based on the particle size which can meet the requirement of the fixed bed catalyst or the fluidized bed catalyst, and the shape of the particles can be at least one of any irregular shape, spheroid, hemispheroid, cylinder, hemicylinder, prism, cube, cuboid, ring, hemiring, hollow cylinder and tooth shape, and preferably at least one of sphere, ring, tooth shape and cylinder shape.
During the preparation of the curing system described in the method (iii) or the method (iv), an additive selected from at least one of a curing accelerator, a dye, a pigment, a colorant, an antioxidant, a stabilizer, a plasticizer, a lubricant, a flow modifier or aid, 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 may be added. The dosage of the used additives is conventional dosage or is adjusted according to the requirements of actual conditions.
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 invention, preferably, in the composite hydrogenation catalyst, the Raney alloy particles contain Raney metal and leachable elements, the weight ratio of the Raney metal to the leachable elements is 1: 99-10: 1, and more preferably 1: 10-4: 1, the Raney metal is selected from at least one of nickel, cobalt, copper and iron, and the leachable elements are selected from at least one of aluminum, zinc and silicon.
According to the method provided by the invention, preferably, in the composite hydrogenation catalyst, the raney alloy particles further comprise a promoter, and the amount of the promoter accounts for 0.01-5wt% 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: mixing a carbonizable organic substance with the Raney alloy particles, and then carrying out die pressing solidification and high-temperature carbonization;
the weight ratio of the Raney alloy particles to the carbonizable organic substance is 1:99 to 99:1, preferably 10:90 to 90:10, and more preferably 25:75 to 75: 25.
Further preferably, the preparation of the composite hydrogenation catalyst comprises the following specific 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 curing formulation commonly used for organic carbonizable substances, to which additives selected from at least one of curing accelerators, dyes, pigments, colorants, antioxidants, stabilizers, plasticizers, lubricants, flow modifiers or auxiliaries, flame retardants, drip retardants, antiblocking agents, adhesion promoters, conductive agents, polyvalent metal ions, impact modifiers, mold release auxiliaries and nucleating agents may be added. The dosage of the additive is conventional dosage or adjusted according to the requirement of actual situation. The prepared solidification system is a liquid system or a powder system, the liquid system can be directly and uniformly stirred, and the powder system can be directly and uniformly blended; the powdery system can be pulverized by any pulverizing apparatus commonly used in industry and then blended uniformly.
In step b, the obtained catalyst precursor can be processed into particles which can be used for reaction in a fixed bed or a fluidized bed 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 requirement of the fixed bed catalyst or the fluidized bed catalyst, and the shape of the particles is selected from at least one of any irregular shape, spheroid, hemispheroid, cylinder, hemicylinder, prism, cube, cuboid, ring, hemiring, hollow cylinder and tooth shape, and is preferably at least one of sphere, ring, tooth shape and cylinder shape.
In step c, the carbonization is generally carried out 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 is carried out for 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 invention, a carbonizable organic substance and the Raney alloy are mixed and then carbonized to obtain a composite of carbon and the Raney alloy, the Raney alloy plays a role in promoting the carbonization process and can ensure that the carbonization is more complete, after the carbonization, the Raney alloy is dispersed in a continuous phase of the carbon and firmly combined with the continuous phase of the carbon, and the continuous phase of the carbon has a porous structure, so that the composite catalyst has 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 Raney alloy is exposed, and therefore the catalyst has high activity.
According to the method provided by the invention, preferably, the polymer material loaded raney nickel catalyst and the composite hydrogenation catalyst are both activated catalysts, and the activation treatment comprises the following steps: and (2) activating the polymer material-loaded Raney nickel catalyst and the composite hydrogenation catalyst by using an alkali solution with the concentration of 0.5-30 wt% at the temperature of 25-95 ℃, and dissolving out at least one of aluminum, zinc and silicon. The alkali solution is NaOH or KOH, and the activation treatment time of the alkali solution is 5 minutes to 72 hours.
The loading of the raney metal in the catalyst can be easily controlled by controlling the addition of the raney alloy particles and/or controlling the activation degree of the catalyst during the preparation of the catalyst, for example, an activated catalyst with a raney metal loading of 1 to 90 wt% (based on 100 wt% of the total weight of the catalyst), preferably an activated catalyst with a raney metal loading of 10 to 80 wt%, more preferably 40 to 80 wt% can be obtained.
The invention has the beneficial effects that: the high molecular material loaded Raney nickel catalyst and the high-activity composite hydrogenation catalyst are sequentially hydrogenated, and the poor ethylene glycol raw material (low ultraviolet light transmittance) can be hydrogenated and upgraded by a two-stage or multi-stage hydrogenation process, so that the unqualified ethylene glycol meets the quality requirement of polyester-grade ethylene glycol; the hydrofining process is stable and efficient, and the ultraviolet light transmittance of the ethylene glycol is obviously improved.
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:
Figure BDA0001138939080000111
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 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. Through hydrofining, the ultraviolet transmittance index is required to meet the requirement of the national standard of industrial ethylene glycol (GB/T4649-2008) on the ultraviolet transmittance of high-quality ethylene glycol:
220nm is more than or equal to 75 percent
275nm greater than or equal to 92%
350nm is more than or equal to 99 percent
Preparation example 1
Preparing a high polymer material loaded Raney nickel catalyst:
(1) extruding polypropylene powder (named as Maoming, F280M) by a double-screw extruder and cutting into particles of phi 3mm multiplied by 3-5 mm;
(2) weighing 100g of polypropylene particles, placing the polypropylene particles in nickel-aluminum alloy particles, wherein the Ni content in the nickel-aluminum alloy is 48 wt%, the Fe metal content is 1.5 wt%, the Cr metal content is 1.5 wt%, the La metal content is 1.0 wt% and the Al metal content is 48 wt%, performing mould pressing for 10min at the temperature of 220 ℃ and the pressure of 7MPa by using a flat vulcanizing instrument, taking out, cooling and sieving to obtain spherical particles, and completely covering the surfaces of the particles with Raney alloy particles to obtain a catalyst, and weighing 420 g;
(3) preparing 400g of 20% NaOH aqueous solution by using deionized water, adding 40g of the catalyst obtained in the step (2), keeping the temperature at 85 ℃, filtering the solution after 8 hours to obtain the activated high polymer material loaded Raney nickel catalyst, washing the catalyst until the nickel metal loading amount is about 60wt% and the catalyst is nearly neutral, and storing the catalyst in the deionized water for later use.
Preparation example 2
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 50g of the epoxy curing system prepared in the step (1) and 150g of nickel-aluminum alloy particles, 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 30min at the temperature of 120 ℃ and the pressure of 7MPa by using a flat-plate vulcanizing instrument, molding for 90min 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 700 ℃ 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 hydrogenation catalyst, and finally storing the catalyst in the deionized water after the nickel metal loading amount in the catalyst is about 50 wt% and the catalyst is washed to be nearly neutral.
Preparation example 3
Preparing a composite hydrogenation catalyst CAT-2:
(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 particles, 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 30min at the temperature of 120 ℃ and the pressure of 7MPa by using a flat-plate vulcanizing instrument, molding for 90min 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 hydrogenation catalyst, finally washing the nickel metal load in the catalyst to be approximately 60wt% to be neutral, and storing the catalyst in the deionized water for later use.
Example 1
Firstly, 50ml of high polymer material-loaded Raney nickel catalyst is loaded into a first fixed bed reactor, and 50ml of hydrogenation catalyst CAT-1 prepared in preparation example 2 is loaded into a second fixed bed reactor; then the ethylene glycol liquid passes through the first fixed bed reactor and the second fixed bed reactor in turn, the inner diameter of the pipe of the reactor is 25mm, the hydrogen flow is 200ml/min, the reaction temperature is 100 ℃, the pressure is 0.5MPa, and the liquid-phase airspeed of the ethylene glycol is 6.0h-1And the ultraviolet transmittance of the raw material before hydrogenation is as follows: 0.6% at 220nm, 45% at 275nm and 70% at 350nm, and the ultraviolet transmittance of the hydrogenated product is measured by using an ultraviolet spectrophotometer and is shown in table 1.
Example 2
50ml of polymer material loaded Raney nickel catalyst is firstly loadedFeeding the mixture into a first fixed bed reactor, and loading 50ml of the hydrogenation catalyst CAT-1 prepared in the preparation example 2 into a second fixed bed reactor, and loading 50ml of the hydrogenation catalyst CAT-2 prepared in the preparation example 3 into a third fixed bed reactor; then the ethylene glycol liquid passes through the first fixed bed reactor, the second fixed bed reactor and the third fixed bed reactor in turn, the pipe inner diameter of the reactor is 25mm, the hydrogen flow is 200ml/min, the reaction temperature is 100 ℃, the pressure is 0.5MPa, and the liquid phase airspeed of the ethylene glycol is 6.0h-1And the ultraviolet transmittance of the raw material before hydrogenation is as follows: 0.6% at 220nm, 45% at 275nm and 70% at 350nm, and the ultraviolet transmittance of the hydrogenated product is measured by using an ultraviolet spectrophotometer and is shown in table 1.
Example 3
Ethylene glycol was hydrorefined according to the method of example 1, except that the amount of the polymer material-supported raney nickel catalyst was 33.3ml, the amount of the hydrogenation catalyst CAT-1 prepared in preparation example 2 was 66.6ml, and the ultraviolet transmittance of the raw material before hydrogenation was: 0.6% at 220nm, 45% at 275nm and 70% at 350nm, and the ultraviolet transmittance of the hydrogenated product is measured by using an ultraviolet spectrophotometer and is shown in table 1.
Example 4
Ethylene glycol was hydrorefined according to the method of example 1, except that the amount of the polymer material-supported raney nickel catalyst was 90ml, the amount of the hydrogenation catalyst CAT-1 prepared in preparation example 2 was 10ml, and the ultraviolet transmittance of the raw material before hydrogenation was: 0.6% at 220nm, 45% at 275nm and 70% at 350nm, and the ultraviolet transmittance of the hydrogenated product is measured by an ultraviolet spectrophotometer and is shown in Table 1.
Example 5
Ethylene glycol was hydrorefined according to the method of example 2, except that the amount of the polymer material-supported raney nickel catalyst was 33.3ml, the amount of the hydrogenation catalyst CAT-1 prepared in preparation example 2 was 66.6ml, the amount of the hydrogenation catalyst CAT-2 prepared in preparation example 3 was 50ml, and the ultraviolet transmittance of the raw material before hydrogenation was: 0.6% at 220nm, 45% at 275nm and 70% at 350nm, and the ultraviolet transmittance of the hydrogenated product is measured by using an ultraviolet spectrophotometer and is shown in table 1.
Example 6
Ethylene glycol was hydrorefined according to the method of example 2, except that the amount of the high-molecular material-supported raney nickel catalyst was 90ml, the amount of the hydrogenation catalyst CAT-1 prepared in preparation example 2 was 10ml, the amount of the hydrogenation catalyst CAT-2 prepared in preparation example 3 was 50ml, and the ultraviolet transmittance of the raw material before hydrogenation was: 0.6% at 220nm, 45% at 275nm and 70% at 350nm, and the ultraviolet transmittance of the hydrogenated product is measured by using an ultraviolet spectrophotometer and is shown in table 1.
Comparative example 1
Ethylene glycol was hydrorefined by the method of example 1, except that the second fixed bed reactor was not provided, and that the ultraviolet transmittance of the raw material before hydrogenation: 0.6% at 220nm, 45% at 275nm and 70% at 350nm, 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 by the method of example 1, except that the first fixed bed reactor was not provided, and that the ultraviolet transmittance of the raw material before hydrogenation: 0.6% at 220nm, 45% at 275nm and 70% at 350nm, and the ultraviolet transmittance of the hydrogenated product is measured by using an ultraviolet spectrophotometer and is shown in table 1.
Comparative example 3
Hydrofinishing of ethylene glycol was carried out as in example 1, except that 50ml of alumina-supported 50% Ni catalyst was charged to the first fixed bed reactor and the feedstock uv transmittance before hydrogenation: 0.6% at 220nm, 45% at 275nm and 70% at 350nm, and the ultraviolet transmittance of the hydrogenated product is measured by using an ultraviolet spectrophotometer and is shown in table 1.
Comparative example 4
Ethylene glycol was hydrorefined by the method of example 2, except that 50ml of γ -alumina-supported 50% Ni catalyst was charged into the second fixed bed reactor and 50ml of γ -alumina-supported 50% Ni catalyst was charged into the third fixed bed reactor, and the uv transmittance of the raw material before hydrogenation: 0.6% at 220nm, 45% at 275nm and 70% at 350nm, and the ultraviolet transmittance of the hydrogenated product is measured by using an ultraviolet spectrophotometer and is shown in table 1.
TABLE 1 UV transmittance of ethylene glycol products obtained by different methods
Figure BDA0001138939080000161
From the UV transmittance results of the ethylene glycol product of Table 1, it can be seen that: the two-stage or three-stage hydrogenation process adopted by the invention can better achieve the reaction effect, so that the hydrofining process is stable and efficient; examples 1 to 6 all demonstrate their effectiveness. As can be seen from comparative examples 1-2, the effect of purifying ethylene glycol after hydrogenation is poor only by using the first-stage hydrogenation process; as can be seen from comparative examples 3-4, the final effect of ethylene glycol purification is also general, with a significant difference from the process of the present invention, using conventional hydrogenation catalysts in the hydrogenation process.
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 (20)

1. A method for hydrofining ethylene glycol is characterized by comprising the following steps:
first-stage hydrogenation: in a first reactor, a raney nickel catalyst loaded by a high molecular material, a glycol crude product and hydrogen are contacted for reaction to obtain a first material flow,
second-stage hydrogenation: in a second reactor, contacting a composite hydrogenation catalyst with the first material flow and hydrogen to react to obtain a second material flow;
optionally, the method further comprises performing at least one stage of hydrogenation after the second stage of hydrogenation, wherein each stage of hydrogenation adopts a composite hydrogenation catalyst;
the polymer material-supported Raney nickel catalyst comprises: the carrier comprises an organic polymer material used as a carrier and Raney alloy particles loaded on the surface of the organic polymer material, wherein the Raney alloy particles are loaded on the surface of the carrier in a form of being partially embedded into the organic polymer material;
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;
in the polymer material loaded Raney nickel catalyst, the Raney alloy particles contain nickel, iron, chromium, lanthanum and aluminum, and the Raney alloy particles comprise the following components in percentage by weight: 30-60wt% of nickel, 0.01-5wt% of iron, 0.01-5wt% of chromium, 0.01-5wt% of lanthanum and 30-60wt% of aluminum.
2. The method of ethylene glycol hydrofining according to claim 1, wherein,
the reaction conditions of each stage of hydrogenation are as follows: the reaction temperature is 50-200 ℃, the reaction pressure is 0.1-8.0MPa, and the reaction space velocity measured by the liquid volume of the crude ethylene glycol is 0.05-20h-1。
3. The method of ethylene glycol hydrofining according to claim 2, wherein,
the reaction conditions of each stage of hydrogenation are as follows: the reaction temperature is 80-120 ℃, the reaction pressure is 0.2-2.0MPa, and the reaction space velocity measured by the liquid volume of the crude product of the ethylene glycol is 0.1-6h-1。
4. The method of ethylene glycol hydrofining according to claim 1, wherein,
when two-stage hydrogenation is carried out, the weight ratio of the high polymer material-loaded Raney nickel catalyst to the composite hydrogenation catalyst is 1: 0.1-2.
5. The method of ethylene glycol hydrofining according to claim 1, wherein,
when three-stage hydrogenation is carried out, the weight of the high molecular material loaded Raney nickel catalyst used in the first-stage hydrogenation is as follows: the weight of the composite hydrogenation catalyst used in the second-stage hydrogenation is as follows: the weight ratio of the composite hydrogenation catalyst used in the third-stage hydrogenation is 1: 0.1-2: 0.1-2.
6. The method of ethylene glycol hydrofining 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.
7. The method of ethylene glycol hydrofining according to claim 6, wherein,
the natural organic high molecular compound is at least one of starch, viscose, lignin and cellulose.
8. The method of ethylene glycol hydrofining according to claim 6, wherein,
the synthetic organic high molecular compound is plastic and/or rubber.
9. The method of ethylene glycol hydrofining according to claim 8, 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.
10. The method of ethylene glycol hydrofining according to claim 1, wherein,
the preparation method of the compound hydrogenation catalyst comprises the following steps: mixing a carbonizable organic substance with the Raney alloy particles, and then carrying out die pressing solidification and high-temperature carbonization;
the weight ratio of the Raney alloy particles to the organic matter capable of being carbonized is 1:99 to 99: 1.
11. The method of ethylene glycol hydrofining according to claim 10, wherein,
the weight ratio of the Raney alloy particles to the organic matter capable of being carbonized is 10: 90-90: 10.
12. The method of ethylene glycol hydrofining according to claim 11, wherein,
the weight ratio of the Raney alloy particles to the carbonizable organic substance is 25:75 to 75: 25.
13. The method of ethylene glycol hydrofining according to claim 1, wherein,
in the composite hydrogenation catalyst, the Raney alloy particles contain Raney metal and leachable elements, the weight ratio of the Raney metal to the leachable elements is 1: 99-10: 1, the Raney metal is selected from at least one of nickel, cobalt, copper and iron, and the leachable elements are selected from at least one of aluminum, zinc and silicon.
14. The method of ethylene glycol hydrofining according to claim 13, wherein,
the weight ratio of Raney metal to leachable elements is 1:10 to 4: 1.
15. The method of ethylene glycol hydrofining according to claim 13, wherein,
in the composite hydrogenation catalyst, the Raney alloy particles also comprise a promoter, and the promoter is selected from at least one of Mo, Cr, Ti, Fe, Pt, Pd, Rh and Ru; the amount of the accelerator accounts for 0.01-5wt% of the total amount of the Raney alloy particles.
16. The method for hydrorefining ethylene glycol according to any one of claims 1 to 5, wherein,
the organic polymer material is selected from plastics or modified products thereof.
17. The method of ethylene glycol hydrofinishing according to claim 16, wherein,
the organic polymer material is at least one of linear polyester, aromatic ring polymer compound, heterocyclic ring polymer compound, fluorine-containing polymer, acrylic resin, urethane, epoxy resin, phenolic resin, urea resin and melamine formaldehyde resin, which are prepared by performing polycondensation reaction on polyolefin, polyamide resin, polycarbonate resin, homopolymerized formaldehyde, copolyoxymethylene, saturated dibasic acid and dihydric alcohol.
18. The method of ethylene glycol hydrofining according to claim 17, wherein,
the organic polymer material is at least one of polyolefin, polyamide resin, epoxy resin and phenolic resin.
19. The method of ethylene glycol hydrofining according to claim 18, wherein,
the organic polymer material is at least one of polypropylene, nylon-6, nylon-66, polystyrene, phenolic resin and epoxy resin.
20. The method for hydrofining ethylene glycol according to any one of claims 1 to 5, wherein the preparation method of the high polymer material supported Raney nickel catalyst is as follows: and under the condition of the forming processing temperature of the organic polymer material or the uncured shaping condition, the organic polymer material coated by the Raney alloy particles is molded.
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