CN112439434B - Glycol hydrofining agent and application thereof - Google Patents
Glycol hydrofining agent and application thereof Download PDFInfo
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- CN112439434B CN112439434B CN201910823775.1A CN201910823775A CN112439434B CN 112439434 B CN112439434 B CN 112439434B CN 201910823775 A CN201910823775 A CN 201910823775A CN 112439434 B CN112439434 B CN 112439434B
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1856—Phosphorus; Compounds thereof with iron group metals or platinum group metals with platinum group metals
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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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The invention relates to a refining agent for removing impurities in crude ethylene glycol and an ethylene glycol hydrofining method, wherein the refining agent comprises a carrier and an active component, and the active component comprises ruthenium; the carrier comprises phosphorus-aluminum mixed oxide, and the refining agent is used in ethylene glycol refining, so that the refined ethylene glycol has high ultraviolet transmittance and insignificant reduction in the storage process, and is stable and long in service life.
Description
Technical Field
The invention relates to a glycol hydrofining agent and a glycol hydrofining method.
Background
Ethylene glycol (EG for short) is an important petrochemical basic organic raw material, and the current industrial production line of ethylene glycol can be mainly divided into a petroleum method and a synthetic gas method. The synthetic gas method mainly uses CO in the synthetic gas to oxidize and couple to generate oxalic ester, and then the oxalic ester is hydrogenated to obtain glycol. In the process of oxalic ester hydrogenation, due to incomplete hydrogenation, a part of byproducts containing carbon-oxygen double bonds which affect the ultraviolet transmittance are generated, and the quality of the final ethylene glycol product is also affected when the byproducts are brought into the subsequent process. Petroleum is mainly ethylene glycol obtained by hydrating ethylene oxide generated after ethylene is oxidized and generated by naphtha cracking, but the production process is mature and stable, but has a plurality of defects, such as ethylene oxidation generates byproducts containing carbon-oxygen double bonds, such as aldehyde, ketone, acid, ester and the like, in addition to ethylene oxide in the production process, ethylene oxide also generates aldehyde byproducts by isomerization, and the species containing carbon-oxygen double bonds influence the transmittance of the ethylene glycol, thereby influencing the quality of the final ethylene glycol product.
More than 100 chemicals are currently derivable from ethylene glycol. The polyester (including polyester fiber, polyester bottle, polyester film, etc.) is the main consumption field of glycol in China, the consumption amount of the polyester accounts for about 90% of the total consumption amount in China, and the polyester accounts for about 10% of the total consumption amount in China, and is used for antifreezing agents, adhesives, paint solvents, cold-resistant lubricating oil, surfactants, etc. Therefore, for removing the impurities containing carbon-oxygen double bonds in the two methods, the ultraviolet transmittance of the ethylene glycol is improved, and the quality of the ethylene glycol product is very important.
The patent WO 9958483 and the patent US 3970711 use activated carbon to treat glycol aqueous solution with relatively low ultraviolet transmittance, so that the ultraviolet transmittance of the glycol obtained after treatment is more than 76% at 220nm, more than 90% at 250nm and more than 92% at 275 nm. Although the ultraviolet transmittance of glycol can be improved by the adsorption of the activated carbon, the activated carbon has short service life, difficult regeneration and high use cost because of limited adsorption capacity, and is not beneficial to industrialization.
How to use the novel refining agent can greatly improve the ultraviolet transmittance of the glycol, can be used for a long time, and meanwhile, the reduction of the UV value is not obvious in the storage process, so that the novel refining agent is a problem to be solved in industrial production practice.
Disclosure of Invention
One of the technical problems to be solved by the invention is to solve the problem of low ultraviolet transmittance of ethylene glycol products in the prior refining technology, and provide a refining agent for removing impurities in crude ethylene glycol, wherein the refining agent is used in ethylene glycol refining, can ensure that the ultraviolet transmittance of the refined ethylene glycol is high, the reduction in the storage process is not obvious, and meanwhile, the refining agent is stable and has long service life.
The second technical problem to be solved by the invention is a preparation method of the refined preparation corresponding to one of the technical problems.
The third technical problem to be solved by the invention is to provide a new ethylene glycol refining method.
In a first aspect, the present invention provides a refining agent for removing impurities from crude ethylene glycol, the refining agent comprising a support and an active component, wherein the active component comprises ruthenium; the support comprises a phosphorus aluminum mixed oxide.
According to some embodiments of the invention, in the phosphorus aluminum mixed oxide, al is in the form of Al 2 O 3 The weight content is 10-80%, P is P 2 O 5 The weight content is 20-90%.
According to some embodiments of the invention, in the phosphorus aluminum mixed oxide, al is in the form of Al 2 O 3 The weight content is 25-65%, P is P 2 O 5 The weight content is 35-75%.
According to some embodiments of the invention, in the phosphorus aluminum mixed oxide, al is in the form of Al 2 O 3 The weight content is 30-70%, P is P 2 O 5 The weight content is 50-70%.
According to some embodiments of the invention, the ruthenium content in the concentrate is 0.1-15wt%, preferably 0.2-10wt%, more preferably 0.5-5.0wt%, such as 0.5%, 1%, 2%, 3%, 4% and 5% and any value in between.
According to some embodiments of the invention, the phosphorus aluminum mixed oxide content in the concentrate is 85-99.9wt%, preferably 90-99.8wt%, more preferably 95-99.5wt%, such as 99.5%, 99%, 98%, 97%, 96% and 95% and any value in between.
According to some embodiments of the invention, in the refining agent, the parts by weight of Ru is preferably 0.5-5 parts, e.g. 0.5 parts, 1 part, 2 parts, 3 parts, 4 parts and 5 parts and any value in between, and the parts by weight of APO is preferably 95-99.5 parts, e.g. 99.5 parts, 99 parts, 98 parts, 97 parts, 96 parts and 95 parts and any value in between.
The second aspect of the present invention provides a method for preparing the above-mentioned agent, comprising the steps of:
(I) Providing a phosphorus-aluminum mixed oxide;
(II) obtaining an impregnation fluid, the impregnation fluid comprising ruthenium salt;
(III) mixing the phosphorus-aluminum mixed oxide with the impregnating solution, drying and roasting to obtain a refined precursor;
(IV) reducing the refiner precursor with a reducing agent to obtain the refiner.
According to some embodiments of the invention, the phosphorus aluminum mixed oxide is prepared by: dissolving aluminum salt and phosphate in water, and mixing to obtain a solution A, and preferably acidizing the solution A by using acid; adjusting the pH value of the solution A to 7-10, preferably 7.5-9 by alkali liquor for reaction to obtain a reaction product; and drying and roasting the reaction product to obtain the phosphorus-aluminum mixed oxide.
According to some embodiments of the invention, the aluminum salt is selected from one or more of aluminum nitrate, aluminum sulfate, and aluminum chloride.
According to some embodiments of the invention, the phosphate is selected from one or more of diammonium phosphate, monoammonium phosphate, sodium dihydrogen phosphate, and potassium dihydrogen phosphate.
According to some embodiments of the invention, the acid is selected from one or more of hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid.
According to some embodiments of the invention, the lye is selected from one or more of sodium hydroxide solution, potassium hydroxide solution and ammonia water.
According to some embodiments of the invention, the firing temperature is 400-600 ℃.
According to some embodiments of the invention, the firing time is 1 to 5 hours.
According to some embodiments of the invention, the ruthenium-containing salt in step (II) is selected from one or more of ruthenium nitrate, ruthenium chloride, ruthenium sulfate, and ruthenium acetate.
According to some embodiments of the invention, the reducing agent is hydrogen, the pressure of the reduction treatment is 0.1-1MPa, and the space velocity of the reducing agent is 200-1000h -1 The reduction temperature is 120-200 ℃ and the reduction time is 2-10h.
According to some preferred modes of the invention, the preparation method of the refining agent comprises the following steps:
1) Aluminum nitrate (Al (NO) 3 ) 3 ·9H 2 O) and diammonium hydrogen phosphate are dissolved in deionized water, stirred for 1 hour to be dissolved, and then concentrated nitric acid is added to acidify the solution to obtain solution A;
2) Adding concentrated ammonia water into the solution A at room temperature to adjust the pH value to 8, filtering the formed precipitate, washing with deionized water, drying overnight at 120 ℃, and roasting at 500 ℃ for 2 hours to obtain phosphorus-aluminum mixed oxide APO;
3) And (3) dissolving ruthenium chloride in deionized water at room temperature to obtain an impregnating solution. Adding the phosphorus-aluminum mixed oxide APO obtained in the step 2) into the impregnating solution, drying the obtained mixture at 120 ℃, and roasting at 500 ℃ for 2 hours to obtain a phosphorus-aluminum mixed oxide loaded Ru refining agent precursor.
4) Loading the Ru refining agent precursor loaded by the phosphorus-aluminum mixed oxide obtained in the step 3) into a fixed bed reactor, reducing with hydrogen, wherein the pressure of the hydrogen is 0.1-1MPa, and the gas hourly space velocity is 200-1000h -1 The reduction temperature is 120-200 ℃, the reduction time is 2-10h, and the Ru/APO catalyst loaded by the phosphorus-aluminum mixed oxide is obtained.
The method adopts an impregnation method to load Ru on a phosphorus-aluminum mixed oxide carrier, and then hydrogen is used for reduction to obtain the metal Ru hydrogenation refined agent loaded by the phosphorus-aluminum mixed oxide. The refining agent has two centers of acidity and hydrogenation activity, and the two centers cooperate with each other, so that the impurities containing carbon-oxygen double bonds in the crude ethylene glycol can be better removed.
In a third aspect, the invention provides a method for hydrofining ethylene glycol, which comprises the steps of introducing crude ethylene glycol and hydrogen to react in the presence of the refining agent.
According to some embodiments of the invention, the reaction temperature is 60-140 ℃, preferably 80-125 ℃, more preferably 100-125 ℃.
According to some embodiments of the invention, the reaction pressure is 0.2-3MPa, preferably 0.5-2.8MPa, more preferably 1.5-2.6MPa.
According to some embodiments of the invention, the crude ethylene glycol has a mass space velocity of 1 to 20 hours -1 Preferably 3 to 9 hours -1 More preferably 3 to 5 hours -1 。
According to some embodiments of the invention, the feed volume ratio (nominal) of the reducing agent to the crude ethylene glycol is in the range of 200 to 1400, preferably 275 to 1200, more preferably 600 to 1200.
The phosphorus-aluminum mixed oxide loaded metal Ru hydrofining agent is used for crude glycol hydrofining, and the crude glycol airspeed is 5h at the reaction temperature of 100 DEG C -1 Under the conditions that the hydrogen pressure is 1.5MPa and the feeding volume ratio (standard state) of hydrogen to crude ethylene glycol is 600, the ultraviolet transmittance of the ethylene glycol after hydrofining is respectively more than 90%, 95% and 99% at 220nm, 275nm and 350nm, the hydrofining activity can be maintained within 400 days, and the ultraviolet transmittance reduction amplitude of the ethylene glycol after refining is less than 5% after 10 days of storage.
The term "standard state" as used herein refers to the standard state of a gas at a temperature of 25℃and a pressure of 101.325 KPa.
In a fourth aspect, the invention provides the use of the above-described concentrate or the above-described process in the purification of ethylene glycol.
Detailed Description
The invention is further illustrated by the following examples. It is essential that the following examples are given for further illustration of the invention and are not to be construed as limiting the scope of the invention.
[ example 1 ]
Preparation of phosphorus-aluminum mixed oxide APO: 58.8g of aluminum nitrate and 22.3g of diammonium phosphate are dissolved in 500mL of deionized water at room temperature, after stirring for 1h, 10mL of concentrated nitric acid is added for acidification, the pH value is continuously regulated to 8 by dropwise adding concentrated ammonia water, the formed precipitate is filtered, washed 3 times with deionized water and dried at 120 DEG COvernight, and drying and roasting at 500 deg.C to obtain phosphorus-aluminum mixed oxide APO-1, wherein the weight content of Al in APO-1 is calculated as Al by ICP-AES 2 O 3 40% by weight of P 2 O 5 And 60% by weight.
[ example 2 ]
The procedure for preparing APO was the same as in example 1, except that 36.8g and 27.9g of aluminum nitrate and diammonium phosphate were used, respectively, to give APO-2 as a phosphorus-aluminum mixed oxide, and the weight content of Al in APO-2 was determined by ICP-AES as Al 2 O 3 25% by weight of P 2 O 5 And 75% by weight.
[ example 3 ]
The procedure for preparing APO was the same as in example 1, except that the amounts of aluminum nitrate and diammonium phosphate used were 95.6g and 13.0g, respectively, to give APO-3, which was measured by ICP-AES, as Al in APO-3 2 O 3 65% by weight of P 2 O 5 And is 35%.
[ example 4 ]
29.4g of carrier APO-1 carrier is dispersed in 100mL of deionized water, then 20mL of aqueous solution containing 1.21g of ruthenium chloride is added, the obtained mixture is dried at 120 ℃, roasting is carried out for 2h at 500 ℃ to obtain a refined preparation precursor, 10g of the precursor is arranged in a fixed bed reactor, the hydrogen pressure is kept at 0.5MPa, the flow rate is 100mL/h (standard state), the reduction temperature is 150 ℃ and the reduction time is 5h, the obtained refined preparation is RAP-1, wherein the weight part of Ru is 2.0, and the weight part of carrier APO is 98.0%.
[ example 5 ]
The preparation method of the hydrofinishing agent is the same as [ example 4 ], except that 29.4g of APO-2 is used as a carrier, and the obtained hydrofinishing agent is RAP-2, wherein the weight part of Ru is 2.0, and the weight part of carrier APO is 98.0.
[ example 6 ]
The preparation method of the hydrofinishing agent is the same as [ example 4 ], except that 29.4g of APO-3 is used as a carrier, and the obtained hydrofinishing agent is RAP-3, wherein the weight part of Ru is 2.0, and the weight part of carrier APO is 98.0.
[ example 7 ]
The preparation method of the hydrofinishing agent is the same as in [ example 4 ], except that 1.81g of ruthenium chloride is used as the metal salt, 29.1g of carrier APO-1 is used, and the obtained hydrofinishing agent is RAP-4, wherein the weight part of Ru is 3.0, and the weight part of carrier APO is 97.0.
[ example 8 ]
The preparation method of the hydrofinishing agent is the same as in [ example 4 ], except that 2.42g of ruthenium chloride is used as the metal salt, 28.8g of carrier APO-1 is used, and the obtained hydrofinishing agent is RAP-5, wherein the weight part of Ru is 4.0, and the weight part of carrier APO is 96.0.
[ example 9 ]
The preparation method of the hydrofinishing agent is the same as that of example 4, except that 29.9g of APO-1 is used as a carrier, 0.30g of ruthenium chloride is used as a metal salt, and the obtained hydrofinishing agent is RAP-6, wherein the weight part of Ru is 0.5, and the weight part of carrier APO is 99.5.
[ example 10 ]
The preparation method of the hydrofinishing agent is the same as that of the [ example 1 ], except that 29.7g of APO1 is used as a carrier, 0.65g of palladium nitrate is used as a metal salt, and the obtained hydrofinishing agent is RAP-7, wherein the weight part of Ru is 1.0, and the weight part of the carrier APO is 99.0.
[ example 11 ]
Charging 1.0 g of the hydrorefining agent RAP-1 prepared in example 4 into a fixed bed reactor, controlling the temperature to be 100 ℃, adding hydrogen, controlling the hydrogen pressure to be 1.5MPa and the flow rate to be 460mL/min, uniformly passing crude ethylene glycol (the mass percent content is 99.8%, the ultraviolet transmittance is 45.1%, 66.3% and 90.5% at 220nm, 275nm and 350nm respectively) through a hydrorefining agent bed layer at the speed of 50.0g/h, and the mass airspeed is 5.0h -1 The volume ratio (standard state) of hydrogen to ethylene glycol was 600, and the obtained purified ethylene glycol was collected, and the ultraviolet transmittance thereof was measured to be 91.6%, 98.0% and 99.9% at 220nm, 275nm and 350nm, respectively. The obtained refined glycol is added with N 2 Protection ofAfter 10 days of storage, the ultraviolet transmittance of the glass is detected to be 90.5%, 97.5% and 99.9% at 220nm, 275nm and 350nm respectively.
Examples 12 to 17
Hydrofining experiments were performed on the hydrofinishing preparation RAP-2-RAP-7 prepared in examples 5-10 under the hydrofinishing conditions adopted in example 11, and the obtained results are shown in Table 1.
TABLE 1
Example 18
The conditions were the same [ example 11 ], except that the feed rate of crude ethylene glycol was 90.0g/h, the amount of hydrogen gas was 800mL/min, and refined ethylene glycol was obtained, and UV transmittance thereof was measured to be 90.4%, 97.6% and 99.9% at 220nm, 275nm and 350nm, respectively. The obtained refined glycol is added with N 2 After 10 days of storage under protection, the ultraviolet transmittance of the material is 89.1%, 97.0% and 99.9% at 220nm, 275nm and 350nm respectively.
[ example 19 ]
The conditions were the same [ example 11 ], except that the feed rate of crude ethylene glycol was 30.0g/h, the amount of hydrogen gas was 280mL/min, and refined ethylene glycol was obtained, and UV transmittance thereof was 92.5%, 98.2% and 99.9% at 220nm, 275nm and 350nm, respectively. The obtained refined glycol is added with N 2 After 10 days of storage under protection, the ultraviolet transmittance of the ultraviolet light is detected to be 91.8%, 98.0% and 99.9% at 220nm, 275nm and 350nm respectively.
[ example 20 ]
The conditions were the same [ example 11 ], except that the reaction temperature was 85℃to give refined ethylene glycol, and the ultraviolet transmittance thereof was found to be 85.3%, 97.0% and 99.7% at 220nm, 275nm and 350nm, respectively. The obtained refined glycol is added with N 2 After 10 days of storage under protection, the ultraviolet transmittance of the material is detected to be 84.2%, 96.5% and 99.7% at 220nm, 275nm and 350nm respectively.
[ example 21 ]
The conditions were the same [ example 11 ], except that the reaction temperature was 125℃to give refined ethylene glycol, whose ultraviolet transmittance was 92.6%, 98.6% and 99.9% at 220nm, 275nm and 350nm, respectively. The obtained refined glycol is added with N 2 After 10 days of storage under protection, the ultraviolet transmittance of the ultraviolet light is detected to be 91.6%, 98.3% and 99.9% at 220nm, 275nm and 350nm respectively.
[ example 22 ]
The conditions were the same [ example 11 ], except that the flow rate of hydrogen was 920mL/min, the feed volume ratio (standard state) of hydrogen to crude ethylene glycol was 1200, and refined ethylene glycol was obtained, and ultraviolet transmittance thereof was measured to be 92.8%, 98.5% and 99.9% at 220nm, 275nm and 350nm, respectively. The obtained refined glycol is added with N 2 After 10 days of storage under protection, the ultraviolet transmittance of the material is detected to be 92.0%, 98.1% and 99.9% at 220nm, 275nm and 350nm respectively.
Example 23
The conditions were the same [ example 11 ], except that the flow rate of hydrogen was 210mL/min, the feed volume ratio (standard state) of hydrogen to crude ethylene glycol was 275, and refined ethylene glycol was obtained, and the ultraviolet transmittance thereof was measured to be 90.1%, 97.1% and 99.9% at 220nm, 275nm and 350nm, respectively. The obtained refined glycol is added with N 2 After 10 days of storage under protection, the ultraviolet transmittance of the material is 89.5%, 97.0% and 99.9% at 220nm, 275nm and 350nm respectively.
[ example 24 ]
The conditions were the same [ example 11 ], except that the pressure of hydrogen was 0.5MPa, to obtain refined ethylene glycol, whose ultraviolet transmittance was found to be 88.1%, 97.1% and 99.9% at 220nm, 275nm and 350nm, respectively. The obtained refined glycol is added with N 2 After 10 days of storage under protection, the ultraviolet transmittance of the fluorescent lamp is 87.5%, 96.9% and 99.8% at 220nm, 275nm and 350nm respectively.
[ example 25 ]
The conditions were the same [ example 11 ], except that the pressure of hydrogen was 2.6MPa, to obtain refined ethylene glycol, whose ultraviolet transmittance was 92.5%, 98.6% and 99.9% at 220nm, 275nm and 350nm, respectively. The obtained refined glycol is treated in the following conditionN 2 After 10 days of storage under protection, the ultraviolet transmittance of the ultraviolet light is detected to be 91.6%, 98.3% and 99.9% at 220nm, 275nm and 350nm respectively.
[ example 26 ]
The lifetime test of the hydrofinishing agent RAP-1 was performed according to the conditions used in [ example 11 ], and the results obtained are shown in Table 2.
TABLE 2
It should be noted that the above-described embodiments are only for explaining the present invention and do not limit the present invention in any way. The invention has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as defined in the appended claims, and the invention may be modified without departing from the scope and spirit of the invention. Although the invention is described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, as the invention extends to all other means and applications which perform the same function.
Claims (20)
1. A refining agent for removing impurities from crude ethylene glycol, the refining agent comprising a carrier and an active component, wherein the active component comprises ruthenium; the carrier comprises phosphorus-aluminum mixed oxide;
in the phosphorus-aluminum mixed oxide, al is Al 2 O 3 The weight content is 10-80%, P is P 2 O 5 The weight content is 20-90%.
2. The concentrate of claim 1, wherein the phosphorusAl is in Al mixed oxide 2 O 3 The weight content is 25-65%; p to P 2 O 5 The weight content is 35-75%.
3. The refining agent according to claim 2, characterized in that in the phosphorus aluminum mixed oxide, al is in the form of Al 2 O 3 The weight content is 30-50%; p to P 2 O 5 The weight content is 50-70%.
4. The concentrate according to claim 1, wherein the ruthenium content in the concentrate is 0.1 to 15wt%.
5. The concentrate according to claim 4, wherein the ruthenium content in the concentrate is 0.2 to 10wt%.
6. The concentrate of claim 5, wherein the ruthenium content in the concentrate is 0.5 to 5.0wt%.
7. A method of preparing the concentrate of any one of claims 1-6, comprising the steps of:
(I) Providing a phosphorus-aluminum mixed oxide;
(II) obtaining an impregnation fluid, the impregnation fluid comprising ruthenium salt;
(III) mixing the phosphorus-aluminum mixed oxide with the impregnating solution, drying and roasting to obtain a refined precursor;
(IV) reducing the refiner precursor with a reducing agent to obtain the refiner.
8. The method of claim 7, wherein the phosphorus aluminum mixed oxide is prepared by: dissolving aluminum salt and phosphate in water, and mixing to obtain a solution A; regulating the pH value of the solution A to 7-10 by alkali liquor to obtain a reaction product; and drying and roasting the reaction product to obtain the phosphorus-aluminum mixed oxide.
9. The method of claim 8, wherein the aluminum salt and the phosphate are dissolved in water and mixed to obtain a solution a, and the solution a is acidified with an acid.
10. The method according to claim 8, wherein the solution A is reacted by adjusting the pH to 7.5-9 with alkali liquor to obtain a reaction product; the alkali liquor is one or more selected from sodium hydroxide solution, potassium hydroxide solution and ammonia water.
11. The method of claim 9, wherein the aluminum salt is selected from one or more of aluminum nitrate, aluminum sulfate, and aluminum chloride; the phosphate is selected from one or more of diammonium hydrogen phosphate, monoammonium phosphate, sodium dihydrogen phosphate and potassium dihydrogen phosphate; the acid is selected from one or more of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid; the roasting temperature is 400-600 ℃; and/or the calcination time is 1-5h.
12. The method according to any one of claims 7 to 11, wherein the ruthenium salt in step (II) is selected from one or more of ruthenium nitrate, ruthenium chloride, ruthenium sulfate and ruthenium acetate; and/or, the number of the groups,
the reducing agent in the step (IV) is hydrogen, the pressure of the reduction treatment is 0.1-1MPa, and the space velocity of the reducing agent is 200-1000h -1 The reduction temperature is 120-200 ℃ and the reduction time is 2-10h.
13. A process for hydrofinishing ethylene glycol comprising reacting crude ethylene glycol with hydrogen in the presence of a refining agent as defined in any one of claims 1 to 6 or a refining agent prepared by a process as defined in any one of claims 7 to 12.
14. The method of claim 13, wherein the reaction temperature is 60-140 ℃; and/or the reaction pressure is 0.2-3 MPa.
15. The method of claim 14, wherein the reaction temperature is 80-125 ℃; and/or the reaction pressure is 0.5-2.8 MPa.
16. The method of claim 14, wherein the reaction temperature is 100-125 ℃; and/or the reaction pressure is 1.5-2.6MPa.
17. The process according to any one of claims 13 to 16, wherein the crude ethylene glycol has a mass space velocity of from 1 to 20h -1 The method comprises the steps of carrying out a first treatment on the surface of the And/or the feed volume ratio of the reducing agent to the crude ethylene glycol is 200-1400.
18. The method of claim 17, wherein the crude ethylene glycol has a mass space velocity of 3-9h -1 The method comprises the steps of carrying out a first treatment on the surface of the And/or the feed volume ratio of the reducing agent to the crude ethylene glycol is 275-1200.
19. The method of claim 18, wherein the crude ethylene glycol has a mass space velocity of 3-5h -1 The method comprises the steps of carrying out a first treatment on the surface of the And/or the feed volume ratio of the reducing agent to the crude ethylene glycol is 600-1200.
20. Use of the refining agent according to any one of claims 1-6 or the refining agent obtained according to the preparation process according to any one of claims 7-12 or the process according to any one of claims 13-19 in ethylene glycol refining.
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