阅读说明：本技术 用于乙二醇精制的稳定剂及其制备方法 (Stabilizer for refining ethylene glycol and preparation method thereof ) 是由 陈梁锋 叶迎春 唐康健 朱俊华 于 2019-09-02 设计创作，主要内容包括：本发明提供了一种用于乙二醇精制的稳定剂,其包括结构为M-CIR的改性树脂,其中,M为金属阳离子,CIR为酸性阳离子交换树脂。这种稳定剂性质稳定,能够将粗乙二醇中的醛类浓度降低至2.5ppm以下,且精制后的乙二醇存储过程中醛类浓度反弹不明显。(The invention provides a stabilizer for ethylene glycol refining, which comprises modified resin with a structure of M-CIR, wherein M is metal cation, and CIR is acidic cation exchange resin. The stabilizer has stable property, can reduce the aldehyde concentration in the crude glycol to below 2.5ppm, and has no obvious rebound of the aldehyde concentration in the storage process of the refined glycol.)

1. A stabilizer for refining glycol comprises modified resin with structure M-CIR, wherein M is metal cation, CIR is acidic cation exchange resin.

2. The stabilizer according to claim 1, characterized in that said M is selected from Zn²⁺、Fe³⁺、Mn²⁺、Co²⁺And Ni²⁺Preferably selected from Zn²⁺And/or Fe³⁺。

3. The stabilizer according to claim 1 or 2, characterized in that the stabilizer comprises, in parts by weight, 1 to 30 parts of M and 70 to 99 parts of CIR; preferably, the stabilizer comprises 2 to 25 parts of M and 75 to 98 parts of CIR; most preferably, the stabilizer comprises 5 to 25 parts of M and 75 to 95 parts CIR.

4. The stabilizer according to any one of claims 1 to 3, wherein the acidic cation exchange resin is a macroporous strong acid cation exchange resin, preferably the macroporous strong acid cation exchange resin is selected from at least one of Amberlyst-15, Amberlyst-35, Amberlyst-36 and NKC-9; and/or the exchange capacity of the acidic cation exchange resin is 2-6 meq/g.

5. A preparation method of a stabilizer for refining ethylene glycol comprises the following steps:

step 1) swelling the acidic cation exchange resin with an aqueous solvent, adding an aqueous solution of a metal salt, mixing, filtering,

and 2) washing and drying the solid filtered in the step 1).

6. The method according to claim 5, wherein the aqueous solvent is deionized water in step 1), preferably the amount of the aqueous solvent is 300-1000% by weight of the acidic cation exchange resin, preferably the swelling temperature is 15-35 ℃ and the time is 2-10h, preferably the mixing time is 2-10h, and/or the drying temperature in step 2) is 100-130 ℃ and the drying time is 20-30 h.

7. The production method according to claim 5 or 6, wherein the acidic cation exchange resin is a strongly acidic cation exchange resin, more preferably at least one of Amberlyst-15, Amberlyst-35, Amberlyst-36 and NKC-9; and/or the exchange capacity of the acidic cation exchange resin is 2-6 meq/g; and/or the metal salt is selected from at least one of nitrate, halide and sulfate.

8. A process for ethylene glycol refining comprising contacting a crude ethylene glycol feedstock with the stabilizer of any one of claims 1-4 or the stabilizer prepared by the process of any one of claims 5-7.

9. According to claim 8The method is characterized in that the contact temperature is 20-80 ℃, preferably 30-60 ℃; and/or the mass space velocity of the crude ethylene glycol raw material is 1-10h^-1Preferably 2-6h^-1。

10. The process of claim 8 or 9, wherein the aldehyde concentration in the crude ethylene glycol feedstock is from 10 to 200 ppm.

Technical Field

The invention belongs to the field of ethylene glycol refining, and particularly relates to a stabilizer for ethylene glycol refining and a preparation method thereof.

Background

Ethylene glycol (EG for short) is an important petrochemical basic organic raw material, and more than 100 chemicals can be derived from the 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. The current route for the industrial production of ethylene glycol can be mainly divided into a petroleum method and a synthesis gas method. The petroleum method is mainly to hydrate ethylene oxide generated after ethylene generated by naphtha cracking is oxidized to obtain ethylene glycol, and although the production process is mature and stable, the production process still has many defects, such as ethylene oxide can be isomerized to aldehyde by-products in the production process, and the ethylene oxide can be oxidized to generate aldehyde substances in the ethylene glycol refining process, and the aldehyde substances can affect the quality of the final ethylene glycol product. 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. Part of aldehydes can be by-produced in the oxalate hydrogenation process, and the quality of the final glycol product can be influenced when the aldehydes are brought into the subsequent process. Therefore, it is very important to remove aldehydes from ethylene glycol products.

Xuezhihui et al (synthetic fibers, 2004, 2, 37-39) used strong acid cation exchange resin to remove aldehydes from petroleum process ethylene glycol at a reaction temperature of 35-55 deg.C and a space velocity of less than 7h^-1In the case of (3), aldehydes in the crude ethylene glycol can be removed to less than 3 ppm. Zhang Yuge et al (CN104356258) used rare earth element modified cation exchange resin to remove aldehydes in ethylene glycol, and reacted at 65 ℃ with the highest aldehyde removal rate of 97%.

Disclosure of Invention

Aiming at the problems of high concentration of residual aldehydes and easy rebound of the aldehyde concentration in the storage process in the prior art of glycol dealdehyding and refining, the invention provides a novel stabilizer for glycol dealdehyding and refining and a method for glycol refining. The method has the characteristics of low concentration of residual aldehydes in the refined ethylene glycol and no rebound of the aldehyde concentration in the storage process.

In a first aspect, the present invention provides a stabilizer for ethylene glycol refining comprising a modified resin having the structure M-CIR, wherein M is a metal cation and CIR is an acidic cation exchange resin.

According to some embodiments of the invention, M is selected from Zn²⁺、Fe³⁺、Mn²⁺、Co²⁺And Ni²⁺At least one of (1).

According to a preferred embodiment of the invention, said M is selected from Zn²⁺And/or Fe³⁺。

According to some embodiments of the invention, the stabilizer comprises, in parts by weight, 1 to 30 parts of M and 70 to 99 parts of CIR.

According to a preferred embodiment of the invention, the stabilizer comprises, in parts by weight, 2 to 25 parts of M and 75 to 98 parts of CIR.

According to a preferred embodiment of the invention, the stabilizer comprises, in parts by weight, 5 to 25 parts of M and 75 to 95 parts of CIR.

According to some embodiments of the invention, the acidic cation exchange resin is a macroporous strong acid cation exchange resin.

According to a preferred embodiment of the present invention, the macroporous strong acid cation exchange resin is at least one of Amberlyst-15, Amberlyst-35, Amberlyst-36 and NKC-9.

According to some embodiments of the invention, the acidic cation exchange resin has an exchange capacity of 2 to 6 meq/g.

In a second aspect, the present invention provides a method for preparing a stabilizer for ethylene glycol purification, comprising:

step 1) swelling the acidic cation exchange resin with an aqueous solvent, adding an aqueous solution of a metal salt, mixing, filtering,

and 2) washing and drying the solid filtered in the step 1).

According to some embodiments of the invention, in step 1), the aqueous solvent is deionized water.

According to some embodiments of the invention, in step 1), the aqueous solvent is used in an amount of 300% to 1000% by weight of the acidic cation exchange resin.

According to some embodiments of the invention, in step 1), the swelling temperature is between 15 and 35 ℃ and the time is between 2 and 10 hours.

According to some embodiments of the invention, in step 1), the mixing time is 2 to 10 h.

According to some embodiments of the present invention, the temperature of the drying in step 2) is 100-130 ℃, and the drying time is 20-30 h.

According to some embodiments of the invention, the acidic cation exchange resin is a strong acid cation exchange resin.

According to a preferred embodiment of the present invention, the acidic cation exchange resin is at least one of Amberlyst-15, Amberlyst-35, Amberlyst-36 and NKC-9.

According to some embodiments of the invention, the acidic cation exchange resin has an exchange capacity of 2 to 6 meq/g.

According to some embodiments of the invention, the metal salt is selected from at least one of nitrate, halide and sulphate.

In a third aspect, the present invention provides a process for ethylene glycol refining comprising contacting a crude ethylene glycol feedstock with a stabilizer according to the first aspect or a stabilizer prepared by the process of the second aspect.

According to some embodiments of the invention, the temperature of the contacting is 20-80 ℃.

According to a preferred embodiment of the invention, the temperature of said contact is between 30 and 60 ℃.

According to some embodiments of the invention, the mass space velocity of the crude ethylene glycol feedstock is in the range of from 1 to 10h^-1。

According to a preferred embodiment of the present invention, the mass space velocity of the crude ethylene glycol feed is in the range of 2 to 6h^-1。

According to some embodiments of the invention, the concentration of aldehydes in the crude ethylene glycol feedstock is from 10 to 200 ppm.

The metal ion modified strong acid cation exchange resin stabilizer is obtained by modifying the strong acid cation exchange resin with metal ions, the stabilizer has stable property, can reduce the aldehyde concentration in crude glycol to below 2.5ppm, and the rebound of the aldehyde concentration in the storage process of refined glycol is not obvious.

Detailed Description

The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.

[ example 1 ]

27.0g of dry macroporous strongly acidic cation exchange resin Amberlyst-15 (exchange capacity 5.2meq/g), 200g of deionized water were charged in a 500mL beaker, and after swelling for 5h, 100mL of Zn (NO: 13.7g of zinc nitrate hexahydrate) was added₃)₂And stirring the solution, performing ion exchange for 5h at room temperature, filtering, washing the filtrate with deionized water for 10 times, and drying in a 110-DEG oven for 24h to obtain the stabilizer MTQ-1 with the structural formula of Zn-Amberlyst-15, wherein the mass fraction of Zn is 9.8, and the mass fraction of Amberlyst-15 is 90.2.

[ example 2 ]

The stabilizer was prepared in the same manner as in example 1 except that 18.6g of iron nitrate nonahydrate was used as the metal salt, and MTQ-2, which is a structural formula of Fe-Amberlyst-15, was obtained, wherein the mass fraction of Fe was 10.0 and the mass fraction of Amberlyst-15 was 90.0.

[ example 3 ]

The stabilizer was prepared in the same manner as in example 1 except that 16.5g of a 50 wt% manganese nitrate solution as a metal salt was used to obtain MTQ-3 having a structural formula of Mn-Amberlyst-15, wherein the mass fraction of Mn was 9.7 and the mass fraction of Amberlyst-15 was 90.3.

[ example 4 ]

The stabilizer was prepared in the same manner as in example 1 except that 11.0g of cobalt chloride hexahydrate, as a metal salt, was used to obtain MTQ-4 as a stabilizer having a structure of Co-Amberlyst-15, wherein the mass fraction of Co was 9.9 and the mass fraction of Amberlyst-15 was 90.1.

[ example 5 ]

The stabilizer was prepared in the same manner as in example 1 except that 10.1g of nickel bromide was used as the metal salt, and MTQ-5, a structural formula of Ni-Amberlyst-15, in which the mass fraction of Ni was 9.8 and the mass fraction of Amberlyst-15 was 90.2, was obtained as the stabilizer.

[ example 6 ]

The stabilizer was prepared in the same manner as in example 1 except that 2.75g of zinc nitrate hexahydrate, 29.4g of dried Amberlyst-35 (ion exchange capacity: 4.8meq/g) as the metal salt, and the resulting stabilizer was MTQ-6 having the formula Zn-Amberlyst-35, wherein Zn was used in a mass fraction of 2.1 and Amberlyst-35 was used in a mass fraction of 97.9.

[ example 7 ]

The stabilizer was prepared in the same manner as in example 1 except that 33.6g of iron nitrate nonahydrate was used as the metal salt, 24.6g of dried NKC-9 (ion exchange capacity: 3.8meq/g) was used as the macroporous cation exchange resin, and MTQ-7 was obtained as the stabilizer having a structural formula of Fe-NKC-9, wherein the mass fraction of Fe was 18.1 and the mass fraction of NKC-9 was 81.9.

[ example 8 ]

The stabilizer was prepared in the same manner as in example 1 except that 20.6g of zinc nitrate hexahydrate, 25.5g of dried Amberlyst-36 (ion exchange capacity: 4.5meq/g) as the metal salt, and 25.5g of the macroporous cation exchange resin were used to obtain MTQ-8 as the stabilizer having the structural formula Zn-Amberlyst-36, wherein Zn-was present in an amount of 14.9 parts by mass and Amberlyst-36 was present in an amount of 85.1 parts by mass.

[ example 9 ]

The stabilizer was prepared in the same manner as in example 1 except that 27.0g of dried Amberlyst-35 (ion exchange capacity of 4.8meq/g) of a macroporous, strongly acidic cation exchange resin was used, and the obtained stabilizer was MTQ-9 and had the structural formula Zn-Amberlyst-35, wherein Zn was present in an amount of 9.8 parts by mass and the mass fraction of Amberlyst-35 was 90.2.

[ example 10 ]

The stabilizer was prepared in the same manner as in example 1 except that 27.0g of dried Amberlyst-36 (ion exchange capacity: 4.5meq/g) of a macroporous, strongly acidic cation exchange resin was used, and MTQ-10, a structural formula of Zn-Amberlyst-36 was obtained, wherein Zn was 9.8 parts by mass and Amberlyst-36 was 90.2 parts by mass.

[ example 11 ]

The stabilizer was prepared in the same manner as in example 1 except that 27.0g of dried NKC-9 (ion exchange capacity: 3.8meq/g) was used as the macroporous, strongly acidic cation exchange resin, and MTQ-11 was obtained as the stabilizer having the structural formula Zn-NKC-9, wherein Zn was 9.8 parts by mass and NKC-9 was 90.2 parts by mass.

[ example 12 ]

The stabilizer was prepared in the same manner as in example 1 except that 27.4g of zinc nitrate hexahydrate, which is a metal salt, was used to obtain MTQ-12 having a structural formula of Zn-Amberlyst-15, wherein Zn was present in an amount of 18.2 parts by mass and Amberlyst-15 was present in an amount of 81.8 parts by mass.

[ example 13 ]

The stabilizer was prepared in the same manner as in example 1 except that 2.52g of zinc nitrate hexahydrate, which is a metal salt, was used to obtain MTQ-13 having a structural formula of Zn-Amberlyst-15, wherein Zn was present in an amount of 2.0 parts by mass and Amberlyst-15 was present in an amount of 98.0 parts by mass.

[ example 14 ]

The stabilizer MTQ-110.0 g prepared in example 1 was charged into a fixed bed reactor, the temperature was controlled at 40 ℃, crude ethylene glycol (99.8% by mass, 65.0ppm by mass of aldehydes) was passed through the stabilizer bed at a rate of 30.0g/h, and the mass space velocity was 3.0h^-1And collecting the obtained refined ethylene glycol to obtain the product with the aldehyde content of 1.0 ppm. The obtained refined ethylene glycol is added in N₂Stored for 10 days under protection, and the aldehyde content is detected to be 1.5 ppm.

[ examples 15 to 26 ]

The stabilizers MTQ-2 to MTQ-13 prepared in examples 2 to 13 were subjected to a dealdehyding test under the dealdehyding conditions employed in example 14, and the results are shown in Table 1.

TABLE 1

Examples	Catalyst and process for preparing same	Residual aldehyde amount (ppm)	Amount of aldehyde (ppm) after storage
				Example 15	MTQ-2	1.1	2.0
Example 16	MTQ-3	1.8	2.5
				Example 17	MTQ-4	1.5	2.3
Example 18	MTQ-5	1.7	3.0
				Example 19	MTQ-6	1.9	2.8
Example 20	MTQ-7	1.5	2.5
				Example 21	MTQ-8	1.2	2.5
Example 22	MTQ-9	1.8	3.0
				Example 23	MTQ-10	1.7	2.9
Example 24	MTQ-11	2.1	3.1
				Example 25	MTQ-12	1.0	1.8
Example 26	MTQ-13	2.5	4.9

[ example 27 ]

Conditions were the same as [ example 14 ] except that the feed rate of the crude ethylene glycol was adjusted50.0g/h and the mass space velocity of 5.0h^-1The content of aldehyde in the obtained refined ethylene glycol is 1.8ppm, and N is₂The aldehyde content after 10 days storage under protection was 2.3 ppm.

[ example 28 ]

The conditions were as in [ example 14 ] except that the feed rate of the crude ethylene glycol was 20.0g/h and the mass space velocity was 2.0h^-1The content of aldehyde in the obtained refined ethylene glycol is 0.8ppm, and N is₂The aldehyde content after 10 days storage under protection was 1.5 ppm.

[ example 29 ]

The conditions were the same as in example 14 except that the reaction temperature was 30 ℃ to obtain refined ethylene glycol having an aldehyde content of 2.1ppm and N₂The aldehyde content after 10 days storage under protection was 2.8 ppm.

[ example 30 ]

The conditions were the same as in example 14 except that the reaction temperature was 60 ℃ to obtain refined ethylene glycol having an aldehyde content of 0.6ppm and N₂The aldehyde content after 10 days storage under protection was 1.2 ppm.

Comparative example 1

The conditions were as in example 14, except that 10.0g of dried macroporous cation exchange resin Amberlyst-15 as a stabilizer was used to give refined ethylene glycol having an aldehyde content of 2.5ppm and N₂The aldehyde content after 10 days storage under protection was 10.5 ppm.

Comparative example 2

The conditions were the same as in example 14 except that 10.0g of dried macroporous cation exchange resin Amberlyst-35 was used as the stabilizer to give refined ethylene glycol having an aldehyde content of 3.0ppm and N₂The aldehyde content after 10 days storage under protection was 15.7 ppm.

[ example 31 ]

The life test of the stabilizer MTQ-1 was carried out under the conditions used in [ example 14 ], and the results obtained are shown in Table 2.

TABLE 2

As can be seen from example 31, when the catalyst is used for the dealdehydizing and refining of ethylene glycol, the reaction temperature is 20-80 ℃, and the mass space velocity is 1-10h^-1Especially the reaction temperature is 35-45 ℃, and the space velocity of the raw material crude glycol is 2-4h^-1Under the conditions of (1), the aldehyde concentration in the ethylene glycol after purification is less than 2.0ppm, even equal to or less than 1.5 ppm. In addition, the stabilizer of the present invention can maintain such dealdehydizing activity for a long period of time (within 400 days), and the aldehyde concentration of the purified ethylene glycol rises by less than 1ppm within 400 days of storage.

The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.