阅读说明：本技术 乙二醇加氢精制剂及其应用 (Ethylene glycol hydrofining agent and application thereof ) 是由 陈梁锋 唐康健 朱俊华 程远琳 王黎敏 于 2019-09-02 设计创作，主要内容包括：本发明涉及一种用于脱除粗乙二醇中杂质的精制剂及乙二醇加氢精制方法,所述精制剂包括载体和活性组分,其中所述活性组分包括钌；所述载体包括磷铝混合氧化物,该精制剂用于乙二醇精制中能够使精制后的乙二醇紫外透过率高、储存过程中降低不明显,同时该精制剂稳定,使用寿命长。(The invention relates to a refining agent for removing impurities in crude glycol and a glycol hydrofining method, wherein the refining agent comprises a carrier and an active component, and the active component comprises ruthenium; the carrier comprises a phosphorus-aluminum mixed oxide, and the refining agent is used for refining ethylene glycol, so 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.)

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 support comprises a phosphorus aluminum mixed oxide.

2. The refining agent according to claim 1, wherein Al in the phosphorus-aluminum mixed oxide is Al₂O₃10-80% by weight, preferably 25-65% by weight, more preferably 30-50% by weight; p and P₂O₅The content is 20 to 90% by weight, preferably 35 to 75% by weight, more preferably 50 to 70% by weight.

3. Refining agent according to claim 1 or 2, characterized in that the ruthenium content in the refining agent is 0.1-15 wt.%, preferably 0.2-10 wt.%, more preferably 0.5-5.0 wt.%.

4. A method for preparing the refining agent as defined in any one of claims 1 to 3, comprising the steps of:

(I) providing a phosphorus-aluminum mixed oxide;

(II) obtaining an impregnation solution comprising ruthenium salt;

(III) mixing the phosphorus-aluminum mixed oxide with the impregnation liquid, drying and roasting to obtain a refining agent precursor;

(IV) reducing the precursor of the refining agent by using a reducing agent to obtain the refining agent.

5. The method according to claim 4, characterized in that the phosphorus-aluminium mixed oxide is prepared by: dissolving aluminum salt and phosphate in water, and mixing to obtain solution A, and preferably acidifying the solution A with acid; adjusting the pH value of the solution A to 7-10, preferably 7.5-9 with alkali liquor to react to obtain a reaction product; drying and roasting the reaction product to obtain the phosphorus-aluminum mixed oxide; preferably, the first and second electrodes are formed of a metal,

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, ammonium dihydrogen 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 alkali liquor is selected from one or more of sodium hydroxide solution, potassium hydroxide solution and ammonia water; the roasting temperature is 400-600 ℃; and/or the roasting time is 1-5 h.

6. The method according to claim 4 or 5, 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 (b) a,

in the step (IV), 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-^-1The reduction temperature is 120-200 ℃, and the reduction time is 2-10 h.

7. A method for hydrorefining ethylene glycol, which comprises reacting crude ethylene glycol with hydrogen gas in the presence of the refining agent as defined in any one of claims 1 to 3 or the refining agent prepared by the method as defined in any one of claims 4 to 6.

8. The process according to claim 7, wherein the reaction temperature is 60-140 ℃, preferably 80-125 ℃, more preferably 100-; and/or the presence of a gas in the gas,

the reaction pressure is 0.2 to 3MPa, preferably 0.5 to 2.8MPa, more preferably 1.5 to 2.6 MPa.

9. The process according to claim 7 or 8, characterized in that the mass space velocity of the crude ethylene glycol is 1-20h^-1Preferably 3-9h^-1More preferably 3-5h^-1(ii) a And/or the presence of a gas in the gas,

the feeding volume ratio of the reducing agent to the crude glycol is 200-.

10. Use of the refining agent according to any one of claims 1 to 3 or the refining agent obtained by the production method according to any one of claims 4 to 6 or the method according to any one of claims 7 to 9 for refining ethylene glycol.

Technical Field

The invention relates to an ethylene glycol hydrofining agent and an ethylene glycol hydrofining method.

Background

Ethylene glycol (EG for short) is an important petrochemical basic organic raw material, and the current industrial production route of ethylene glycol mainly comprises two methods, namely a petroleum method and a synthesis gas method. The synthesis gas method mainly comprises the steps of oxidizing and coupling CO in the synthesis gas to generate oxalate, and then hydrogenating the oxalate to obtain the ethylene glycol. In the hydrogenation process of oxalate, partial byproducts containing carbon-oxygen double bonds and influencing ultraviolet transmittance are generated due to incomplete hydrogenation, and the byproducts are carried to subsequent processes and influence the quality of the final ethylene glycol product. The petroleum method is mainly to hydrate ethylene oxide generated after ethylene generated by naphtha cracking is oxidized to obtain ethylene glycol, although the production process is mature and stable, the production process has many defects, for example, ethylene oxidation in the production process can generate byproducts containing carbon-oxygen double bonds such as aldehyde, ketone, acid, ester and the like besides ethylene oxide, ethylene oxide can also be isomerized to aldehyde byproducts, and the species containing the carbon-oxygen double bonds can influence the permeability of ethylene glycol, thereby influencing the quality of the final ethylene glycol product.

Currently more than 100 chemicals can be derived from ethylene glycol. The polyester (including polyester fiber, polyester bottle, polyester film, etc.) is the main consumption field of ethylene glycol in China, the consumption amount of the polyester accounts for about 90% of the total domestic consumption amount, and about 10% of the polyester is used for an antifreezing agent, an adhesive, a paint solvent, cold-resistant lubricating oil, a surfactant, etc. Therefore, the method is very important for removing impurities containing carbon-oxygen double bonds in the two methods, thereby improving the ultraviolet transmittance of the ethylene glycol and improving the quality of the ethylene glycol product.

WO 9958483 and US 3970711 disclose the use of activated carbon to treat aqueous ethylene glycol solutions having relatively low UV transmittance, such that the UV transmittance of the ethylene glycol obtained after treatment is greater than 76% at 220nm, greater than 90% at 250nm, and greater than 92% at 275 nm. Although the ultraviolet transmittance of the ethylene glycol can be improved by the activated carbon adsorption, the activated carbon has limited adsorption capacity, so the activated carbon has short service life, difficult regeneration and high use cost, and is not beneficial to industrialization.

How to use the novel refining agent, the ultraviolet transmittance of the glycol can be greatly improved, the glycol can be used for a long time, and simultaneously, the UV value is not obviously reduced in the storage process, so that the method is a problem to be solved urgently in the industrial production practice.

Disclosure of Invention

One of the technical problems to be solved by the invention is to provide a refining agent for removing impurities in crude glycol, which is used for refining the glycol, so that the ultraviolet transmittance of the refined glycol is high, the reduction in the storage process is not obvious, and 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 refining agent corresponding to the first technical problem.

The third technical problem to be solved by the invention is to provide a novel method for refining ethylene glycol.

The invention provides a refining agent for removing impurities from crude ethylene glycol, which comprises a carrier 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, the Al in the phosphorus-aluminum mixed oxide is Al₂O₃10-80% by weight of P, P is P₂O₅The weight content is 20-90%.

According to some embodiments of the invention, the Al in the phosphorus-aluminum mixed oxide is Al₂O₃25-65% by weight of P, P is P₂O₅The weight content is 35-75%.

According to some embodiments of the invention, the Al in the phosphorus-aluminum mixed oxide is Al₂O₃The weight percentage of P is 30-70 percent, and P is P₂O₅The weight content is 50-70%.

According to some embodiments of the invention, the ruthenium content in the refining agent is 0.1-15 wt%, preferably 0.2-10 wt%, more preferably 0.5-5.0 wt%, such as 0.5%, 1%, 2%, 3%, 4% and 5% and any value in between.

According to some embodiments of the invention, the content of the phosphorus-aluminium mixed oxide in the refining agent is 85-99.9 wt.%, preferably 90-99.8 wt.%, more preferably 95-99.5 wt.%, such as 99.5%, 99%, 98%, 97%, 96% and 95% and any value in between.

According to some embodiments of the invention, the Ru is preferably present in the refining agent in an amount of 0.5 to 5 parts by weight, such as 0.5, 1, 2, 3, 4 and 5 parts by weight and any value therebetween, and the APO is preferably present in an amount of 95 to 99.5 parts by weight, such as 99.5, 99, 98, 97, 96 and 95 parts by weight and any value therebetween.

The second aspect of the invention provides a preparation method of the refining agent, which comprises the following steps:

(I) providing a phosphorus-aluminum mixed oxide;

(II) obtaining an impregnation solution comprising ruthenium salt;

(III) mixing the phosphorus-aluminum mixed oxide with the impregnation liquid, drying and roasting to obtain a refining agent precursor;

(IV) reducing the precursor of the refining agent by using a reducing agent to obtain the refining agent.

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 solution A, and preferably acidifying the solution A with acid; adjusting the pH value of the solution A to 7-10, preferably 7.5-9 with alkali liquor to react 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 aluminium salt is selected from one or more of aluminium nitrate, aluminium sulphate and aluminium chloride.

According to some embodiments of the invention, the phosphate salt is selected from one or more of diammonium phosphate, monoammonium phosphate, monosodium phosphate and monopotassium 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 a sodium hydroxide solution, a potassium hydroxide solution and ammonia.

According to some embodiments of the invention, the calcination 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 present 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^-1The reduction temperature is 120-200 ℃, and the reduction time is 2-10 h.

According to some preferred embodiments of the present invention, the refining agent is prepared by the following steps:

1) aluminum nitrate (Al (NO) was added at room temperature₃)₃·9H₂O) 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 a 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 at 120 ℃ overnight, and roasting at 500 ℃ for 2h to obtain a phosphorus-aluminum mixed oxide APO;

3) ruthenium chloride was dissolved in deionized water at room temperature to obtain a dip. Adding the phosphorus-aluminum mixed oxide APO obtained in the step 2) into the impregnation liquid, drying the obtained mixture at 120 ℃, and then roasting at 500 ℃ for 2h to obtain the Ru refining agent precursor loaded by the phosphorus-aluminum mixed oxide.

4) The precursor of the Ru refining agent loaded by the phosphorus-aluminum mixed oxide obtained in the step 3) is loaded in a fixed bed reactor and is reduced by hydrogen, the pressure of the hydrogen is 0.1-1MPa, and the gas hourly space velocity is 200-^-1The reduction temperature is 120-.

The method adopts an impregnation method to load Ru on a phosphorus-aluminum mixed oxide carrier, and then uses hydrogen to reduce the Ru to obtain the metal Ru hydrofining agent loaded on the phosphorus-aluminum mixed oxide. The refining agent has two centers of acidity and hydrogenation activity, and the two centers have synergistic effect, so that impurities containing carbon-oxygen double bonds in the crude glycol can be better removed.

In a third aspect, the invention provides a method for hydrorefining ethylene glycol, which comprises introducing crude ethylene glycol and hydrogen to react in the presence of the refining agent.

According to some embodiments of the present 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 between 0.2 and 3MPa, preferably between 0.5 and 2.8MPa, more preferably between 1.5 and 2.6 MPa.

According to some embodiments of the invention, the mass space velocity of the crude ethylene glycol is from 1 to 20h^-1Preferably 3-9h^-1More preferably 3-5h^-1。

According to some embodiments of the present invention, the feed volume ratio (standard state) of the reducing agent to the crude ethylene glycol is 200-.

The metal Ru hydrofining agent loaded by the phosphorus-aluminum mixed oxide is used for hydrofining crude glycol, and the reaction temperature is 100 ℃, the airspeed of the crude glycol is 5h^-1Under the conditions that the hydrogen pressure is 1.5MPa and the feeding volume ratio (standard state) of hydrogen to crude glycol is 600, the ultraviolet transmittance of the hydrofined glycol 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 refined glycol is less than 5% after the refined glycol is stored for 10 days.

The term "standard state" as used in the present invention refers to the standard state of a gas at a temperature of 25 ℃ and a pressure of 101.325 KPa.

The invention provides the application of the refining agent or the method in the refining of the glycol.

Detailed Description

The invention is further illustrated by the following examples. It is to be noted that the following examples are only for the purpose of further illustrating the present invention and should not be construed as limiting the scope of the present invention.

[ example 1 ]

Preparation of phosphorus-aluminum mixed oxide APO: at room temperature, 58.8g of aluminum nitrate and 22.3g of diammonium hydrogen phosphate are dissolved in 500mL of deionized water, stirred for 1h, added with 10mL of concentrated nitric acid for acidification, then continuously dropwise added with concentrated ammonia water to adjust the pH value to 8, formed precipitate is filtered, washed for 3 times by deionized water, dried at 120 ℃ overnight, dried and roasted at 500 ℃ to obtain phosphorus-aluminum mixed oxide APO-1, and the weight content of Al in the APO-1 is determined by ICP-AES (inductively coupled plasma-atomic emission spectrometry)₂O₃40% by weight of P, the content of P being expressed as P₂O₅The amount was 60%.

[ example 2 ]

Preparation of an aluminum-phosphorus mixed oxide APO the procedure was the same as in example 1 except that 36.8g and 27.9g of aluminum nitrate and 27.9g of diammonium phosphate were used, respectively, to obtain an aluminum-phosphorus mixed oxide APO-2, and the weight content of Al in the APO-2 was determined by ICP-AES as Al₂O₃Calculated as 25%, the weight content of P is calculated as P₂O₅The content was found to be 75%.

[ example 3 ]

Preparation of an AlP-APO was carried out in the same manner as in example 1 except that 95.6g and 13.0g of each of aluminum nitrate and diammonium hydrogen phosphate were used to obtain an AlP-APO-3, and the weight content of Al in the APO-3 was determined by ICP-AES (inductively coupled plasma-atomic emission Spectrometry), and the weight content of Al in the APO-3 was determined as Al₂O₃Calculated as 65%, the weight content of P is calculated as P₂O₅The weight is 35%.

[ example 4 ]

29.4g of carrier APO-1 is dispersed in 100mL of deionized water, 20mL of aqueous solution containing 1.21g of ruthenium chloride is added, the obtained mixture is dried at 120 ℃, the mixture is roasted at 500 ℃ for 2h to obtain a precursor of a refining agent, 10g of the precursor is put 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 ℃, the reduction time is 5h, the obtained refining agent is RAP-1, the weight part of Ru is 2.0, and the weight part of carrier APO is 98.0%.

[ example 5 ]

The hydrofining agent was prepared in the same manner as in example 4 except that 29.4g of APO-2 as the carrier was used and RAP-2 was obtained as the hydrofining agent, wherein 2.0 parts by weight of Ru and 98.0 parts by weight of APO as the carrier.

[ example 6 ]

The hydrofining agent was prepared in the same manner as in example 4 except that 29.4g of APO-3 as the carrier was used and RAP-3 was obtained as the hydrofining agent, wherein 2.0 parts by weight of Ru and 98.0 parts by weight of APO as the carrier.

[ example 7 ]

The hydrofining agent was prepared in the same manner as in example 4 except that 1.81g of ruthenium chloride was used as the metal salt, 29.1g of APO-1 was used as the carrier, and RAP-4 was used as the hydrofining agent, wherein 3.0 parts by weight of Ru and 97.0 parts by weight of APO was used as the carrier.

[ example 8 ]

The hydrofining agent was prepared in the same manner as in example 4 except that 2.42g of ruthenium chloride was used as the metal salt, 28.8g of APO-1 was used as the carrier, and RAP-5 was used as the hydrofining agent, wherein 4.0 parts by weight of Ru and 96.0 parts by weight of APO was used as the carrier.

[ example 9 ]

The hydrofining agent was prepared in the same manner as in example 4 except that 29.9g of APO-1 as the carrier and 0.30g of ruthenium chloride as the metal salt were used, and the resulting hydrofining agent was RAP-6, in which 0.5 part by weight of Ru and 99.5 parts by weight of APO as the carrier were used.

[ example 10 ]

The hydrofining agent was prepared in the same manner as in example 1, except that 29.7g of APO1 as the carrier and 0.65g of palladium nitrate as the metal salt were used, and the resulting hydrofining agent was RAP-7 in which 1.0 part by weight of Ru and 99.0 parts by weight of APO as the carrier were used.

[ example 11 ]

110.0 g of the hydrofining agent RAP (Rap-Raphnia) prepared in example 4 was charged into a fixed bed reactor, the temperature was controlled at 100 ℃, hydrogen was added, the pressure of hydrogen was controlled at 1.5MPa, and the stream was cooledThe speed is 460mL/min, crude glycol (the mass percentage content is 99.8%, the ultraviolet transmittance is 45.1%, 66.3% and 90.5% at 220nm, 275nm and 350nm respectively) is uniformly passed through a hydrofining agent bed layer at the speed of 50.0g/h, and the mass space velocity is 5.0h^-1And the volume ratio (standard state) of the hydrogen to the ethylene glycol is 600, and the obtained refined ethylene glycol is collected, and the ultraviolet transmittance of the refined ethylene glycol is respectively 91.6%, 98.0% and 99.9% at 220nm, 275nm and 350 nm. The obtained refined ethylene glycol is added in N₂The product is stored for 10 days under protection, and the ultraviolet transmittance of the product is respectively 90.5%, 97.5% and 99.9% at 220nm, 275nm and 350 nm.

[ examples 12 to 17 ]

The hydrorefining agents RAP-2-RAP-7 prepared in examples 5 to 10 were subjected to a hydrorefining experiment under the hydrorefining conditions employed in example 11, and the results are shown in Table 1.

TABLE 1

[ example 18 ]

The conditions were the same as in example 11 except that the feeding rate of the crude ethylene glycol was 90.0g/h and the amount of hydrogen fed was 800mL/min, to obtain refined ethylene glycol, whose ultraviolet transmittances were measured to be 90.4%, 97.6% and 99.9% at 220nm, 275nm and 350nm, respectively. The obtained refined ethylene glycol is added in N₂The product is stored for 10 days under protection, and the ultraviolet transmittance of the product is respectively 89.1%, 97.0% and 99.9% at 220nm, 275nm and 350 nm.

[ example 19 ]

The conditions were the same as in example 11 except that the feeding rate of the crude ethylene glycol was 30.0g/h and the amount of hydrogen fed was 280mL/min, to obtain refined ethylene glycol, whose ultraviolet transmittances were measured to be 92.5%, 98.2% and 99.9% at 220nm, 275nm and 350nm, respectively. The obtained refined ethylene glycol is added in N₂The product is stored for 10 days under protection, and the ultraviolet transmittance of the product is respectively 91.8%, 98.0% and 99.9% at 220nm, 275nm and 350 nm.

[ example 20 ]

The conditions were the same as in example 11 except that the reaction temperature was 85 ℃ to obtain refined ethylene glycol whose ultraviolet transmittances were 85.3%, 97.0% and 99.7% at 220nm, 275nm and 350nm, respectively. The obtained refined ethylene glycol is added in N₂The product is stored for 10 days under protection, and the ultraviolet transmittance of the product is respectively 84.2%, 96.5% and 99.7% at 220nm, 275nm and 350 nm.

[ example 21 ]

The conditions were the same as in example 11 except that the reaction temperature was 125 ℃ to obtain refined ethylene glycol, and the ultraviolet transmittances thereof were measured to be 92.6%, 98.6% and 99.9% at 220nm, 275nm and 350nm, respectively. The obtained refined ethylene glycol is added in N₂The product is stored for 10 days under protection, and the ultraviolet transmittance of the product is respectively 91.6%, 98.3% and 99.9% at 220nm, 275nm and 350 nm.

[ example 22 ]

The conditions were the same as in example 11 except that the flow rate of hydrogen was 920mL/min and the feed volume ratio (standard) of hydrogen to crude ethylene glycol was 1200 to give refined ethylene glycol, which was measured to have UV transmittances of 92.8%, 98.5% and 99.9% at 220nm, 275nm and 350nm, respectively. The obtained refined ethylene glycol is added in N₂The product is stored for 10 days under protection, and the ultraviolet transmittance of the product is respectively 92.0%, 98.1% and 99.9% at 220nm, 275nm and 350 nm.

[ example 23 ]

The conditions were the same as in example 11 except that the flow rate of hydrogen was 210mL/min and the feed volume ratio (standard) of hydrogen to crude ethylene glycol was 275 to obtain refined ethylene glycol, which was measured to have UV transmittances of 90.1%, 97.1% and 99.9% at 220nm, 275nm and 350nm, respectively. The obtained refined ethylene glycol is added in N₂The product is stored for 10 days under protection, and the ultraviolet transmittance of the product is respectively 89.5%, 97.0% and 99.9% at 220nm, 275nm and 350 nm.

[ example 24 ]

The conditions were the same as in example 11 except that the pressure of hydrogen was 0.5MPa, and refined ethylene glycol was obtained, and the ultraviolet transmittances thereof were measured to be 88.1%, 97.1% and 99.9% at 220nm, 275nm and 350nm, respectively. Will obtainRefined ethylene glycol in N₂The product is stored for 10 days under protection, and the ultraviolet transmittance of the product is respectively 87.5%, 96.9% and 99.8% at 220nm, 275nm and 350 nm.

[ example 25 ]

The conditions were the same as in example 11 except that the pressure of hydrogen was 2.6MPa, and refined ethylene glycol was obtained, and the ultraviolet transmittances thereof were measured to be 92.5%, 98.6% and 99.9% at 220nm, 275nm and 350nm, respectively. The obtained refined ethylene glycol is added in N₂The product is stored for 10 days under protection, and the ultraviolet transmittance of the product is respectively 91.6%, 98.3% and 99.9% at 220nm, 275nm and 350 nm.

[ example 26 ]

The life test of the hydrofinishing agent RAP-1 was carried out under the conditions used in [ example 11 ], and the results obtained are shown in Table 2.

TABLE 2

It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not set any limit to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.