WO2018233551A1 - Catalyst for preparing methoxy ethyl tert-butyl ether by reaction of ethylene glycol monomethyl ether and isobutylene, preparation method therefor and use thereof - Google Patents

Catalyst for preparing methoxy ethyl tert-butyl ether by reaction of ethylene glycol monomethyl ether and isobutylene, preparation method therefor and use thereof Download PDF

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WO2018233551A1
WO2018233551A1 PCT/CN2018/091298 CN2018091298W WO2018233551A1 WO 2018233551 A1 WO2018233551 A1 WO 2018233551A1 CN 2018091298 W CN2018091298 W CN 2018091298W WO 2018233551 A1 WO2018233551 A1 WO 2018233551A1
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catalyst
weight
isobutylene
zeolite molecular
ethylene glycol
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PCT/CN2018/091298
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French (fr)
Chinese (zh)
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袁兴东
京堂真大
柴剑宇
高潮
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高化学技术株式会社
袁兴东
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Publication of WO2018233551A1 publication Critical patent/WO2018233551A1/en

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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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
    • B01J29/14—Iron group metals or copper
    • B01J29/146—Y-type faujasite
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/085—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • B01J29/088—Y-type faujasite
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
    • B01J29/14—Iron group metals or copper
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/76—Iron group metals or copper
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/05—Preparation of ethers by addition of compounds to unsaturated compounds
    • C07C41/06—Preparation of ethers by addition of compounds to unsaturated compounds by addition of organic compounds only
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
    • C07C43/04—Saturated ethers
    • C07C43/10—Saturated ethers of polyhydroxy compounds
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself

Definitions

  • the present invention relates to a catalyst for reacting ethylene glycol monomethyl ether with isobutylene to prepare methoxyethyl tert-butyl ether, a preparation method and use thereof, and ethylene glycol monomethyl ether in the presence of the catalyst A process for preparing methoxyethyl tert-butyl ether by reaction with isobutylene.
  • Methoxyethyl tert-butyl ether is a good solvent that is miscible with a variety of organic compounds. In addition, due to its good solubility and stability, and high cetane number, it can be used as a diesel additive to reduce soot emissions. TBME has a low freezing point and can also be used as an antifreeze for aviation diesel. Although the scope of application of TBME in the world is not too wide, there are no production and sales examples in China, but the synthesis and application research of TBME is a very significant topic.
  • GB1587272A describes a method for preparing TBME by reacting ethylene glycol monomethyl ether and isobutylene in a batch reactor using a sulfonic acid resin catalyst.
  • the catalyst and ethylene glycol monomethyl ether are charged into the reaction vessel.
  • the reaction was carried out by introducing isobutylene at 85 ° C and 2.5 bar.
  • the weight ratio of ethylene glycol monomethyl ether to isobutylene was 4:3, and the final conversion of isobutylene was 70%. This document does not describe the selectivity of the product and the repeated use of the catalyst.
  • EP0055045A1 considers the use of a sulfonic acid resin as a catalyst for the etherification reaction of isobutylene with an alcohol, which has the disadvantage of poor thermal stability of the catalyst, and has developed a catalyst of Nu-2 molecular sieve for the etherification reaction of isobutylene with an alcohol.
  • the alcohol mentioned in the literature comprises ethylene glycol monomethyl ether, under the action of a Nu-2 catalyst, 0.21 mol of isobutylene and 0.25 mol of ethylene glycol monomethyl ether in a batch reactor at 90 ° C and spontaneously The reaction under pressure resulted in a conversion of isobutylene of 42.3% and a selectivity of TBME of 96.5%. This document does not report repeated use of the catalyst.
  • the resin catalyst used in GB1587272A has relatively high activity, but the defect of poor thermal stability of the resin catalyst is obvious.
  • EP0055045A1 uses molecular sieve instead of sulfonic acid resin catalyst, the thermal stability of the catalyst is improved, but the conversion rate of isobutylene is relatively low.
  • the present invention provides a novel catalyst for preparing TBME by reacting ethylene glycol monomethyl ether with isobutylene, which is environmentally friendly, has high isobutene conversion and TBME selectivity, and is good. Stability and regeneration performance.
  • a catalyst for preparing TBME by reacting ethylene glycol monomethyl ether with isobutylene comprises the following components in weight percentage:
  • the sum of the components is added up to 100% by weight.
  • Another object of the present invention is to provide a process for the preparation of the catalyst of the present invention which comprises the steps of:
  • step (3) kneading the modified zeolite molecular sieve obtained in the step (2) with a carrier or a carrier precursor, a molding aid, an acid and water, followed by molding, drying, calcining, crushing and sieving to obtain solid particles.
  • the amount of each component is such that, based on the total weight of the catalyst, the catalyst comprises the following components:
  • the sum of the components is added up to 100% by weight.
  • a further object of the present invention is to provide a process for the preparation of methoxyethyl tert-butyl ether which comprises contacting ethylene glycol monomethyl ether and isobutylene with a catalyst of the invention under etherification conditions.
  • a further object of the invention is to provide the use of the catalyst of the invention in the preparation of methoxyethyl tert-butyl ether.
  • the invention provides a catalyst for the preparation of TBME from the reaction of ethylene glycol monomethyl ether with isobutylene, comprising, by weight percent, the following components:
  • the sum of the components is added up to 100% by weight.
  • the catalyst according to the invention comprises preferably from 55 to 90% by weight, more preferably from 65 to 88% by weight, of component a).
  • the catalyst according to the invention comprises preferably from 10 to 45% by weight, more preferably from 12 to 35% by weight, of component b).
  • the content of the metal and/or its oxide in the catalyst of the invention is preferably from 0.1 to 3.0% by weight, based on the total weight of the catalyst.
  • the zeolite molecular sieve used in the catalyst of the present invention is based on zeolite molecular sieves well known to those skilled in the art, for example, zeolite molecules are screened from one or more of USY zeolite molecular sieves, beta zeolite molecular sieves and mordenite molecular sieves, still more preferably USY zeolite molecular sieves and / or beta zeolite molecular sieves, particularly preferably USY zeolite molecular sieves.
  • the present invention has no particular requirement for the source of the zeolite molecular sieve, and is commercially available or can be obtained by a method for synthesizing a zeolite molecular sieve by the prior art.
  • the zeolite molecular sieve is a USY zeolite molecular sieve.
  • the metal in component a) of the invention is preferably Ni.
  • the type of the carrier to be used in the present invention is not particularly limited, and may be selected according to actual needs.
  • the carrier may be selected from one or more of ⁇ -Al 2 O 3 and silica.
  • Another aspect of the invention provides a method of preparing a catalyst of the invention, the method comprising:
  • step (3) kneading the modified zeolite molecular sieve obtained in the step (2) with a carrier or a carrier precursor, a molding aid, an acid and water, followed by molding, drying, calcining, crushing and sieving to obtain solid particles.
  • the amount of each component is such that, based on the total weight of the catalyst, the catalyst comprises the following components:
  • the sum of the components is added up to 100% by weight.
  • the present invention has no particular requirement for the conditions of contacting the aqueous solution of the water-soluble metal salt with the H-type zeolite molecular sieve of the step (1) in the step (2).
  • the contact conditions may include: the contact temperature may be 50-150 ° C. Preferably, the temperature is from 55 to 120 ° C; the contact time may be from 2 to 10 hours, preferably from 3 to 8 hours.
  • step (2) has no particular requirements for other operations in step (2) and can be carried out using methods well known in the art.
  • the present invention has no particular requirement for the conditions of kneading in the step (3).
  • the kneading conditions may include: the kneading temperature may be 20-50 ° C, preferably 25-45 ° C; the kneading time may be 20-90 minutes, It is preferably 25-45 minutes.
  • the present invention also includes the steps of forming, drying and calcining after kneading in the step (3).
  • the method of molding, the method of drying, and the method of firing can be carried out using methods well known in the art.
  • the drying in the step (3) of the present invention may be a conventional drying condition for preparing the H-type zeolite molecular sieve.
  • the drying temperature may be 50-250 ° C, preferably 100-200 ° C; and the drying time may be 6-120 hours. It is preferably 10-96 hours.
  • the calcination in the step (3) of the present invention may be a conventional calcination condition for preparing a zeolite H molecular sieve.
  • the calcination temperature may be 500 to 750 ° C; preferably 520 to 650 ° C; the calcination time may be 1 to 10 hours, preferably 3 to 8 hours; and the calcination atmosphere may be air or an inert gas such as N 2 .
  • the acid used in the step (3) is not particularly limited, and includes at least one of a mineral acid (e.g., nitric acid, hydrochloric acid, sulfuric acid, etc.) or an organic acid (formic acid, acetic acid, propionic acid, oxalic acid, etc.).
  • the molding aid may be at least one selected from the group consisting of glutinous rice flour, polyvinyl alcohol, and polyethylene glycol.
  • the present invention is not particularly limited to the crushing and sieving step in the step (3), and any method known in the art can be used.
  • the kind and amount of the H-type zeolite molecular sieve, the SiO 2 /Al 2 O 3 molar ratio, the kind and amount of the carrier are as described above, and will not be described herein.
  • the carrier precursor at least one selected from the group consisting of aluminum sol, pseudoboehmite, silica sol, and clay may be selected.
  • the molar ratio of ethylene glycol monomethyl ether to isobutylene is not particularly limited, and for example, the molar ratio may be from 0.7 to 10:1, preferably from 0.8 to 5:1, more preferably from 0.9 to 2:1. .
  • the conditions for contacting ethylene glycol monomethyl ether and isobutylene with a catalyst are not particularly limited, and for example, the conditions of the contact may include: a contact temperature of 30 to 100 ° C, and/or a contact pressure of 0.01 to 5.0.
  • the MPa, and/or mass space velocity is 0.1-10 h -1 .
  • the contact temperature is 50-70 ° C, and/or the contact pressure is 0.1-3.0 MPa, and/or the mass space velocity is 0.1-5 h -1 .
  • the form of the reactor to be contacted is not particularly limited, and the reactor may be a fixed bed reactor, a slurry bed reactor, or a batch reactor.
  • the monolithic reactor refers to a reactor using a monolithic catalyst of a monolith, and preferably the reactor is a fixed bed.
  • a further aspect of the invention provides the use of a catalyst of the invention in the preparation of methoxyethyl tert-butyl ether.
  • Example 1 The same experimental conditions as in Example 1 were employed except that Ni(NO 3 ) 2 ⁇ 6H 2 O was not added. The performance was evaluated and the results are shown in Table 1.
  • Example 1 The same experimental conditions as in Example 1 were employed except that the SiO 2 /Al 2 O 3 molar ratios of the USY zeolite molecular sieves were changed to 30, 80 and 110, respectively, and their properties were evaluated. The results are shown in Table 1.
  • Example 1 The same experimental conditions as in Example 1 were employed except that 8.8 g of Ni(NO 3 ) 2 ⁇ 6H 2 O was changed to 8.88 g of Zn(NO 3 ) 2 ⁇ 6H 2 O. The performance was evaluated and the results are shown in Table 1.
  • Example 1 The same experimental conditions as in Example 1 were employed except that 8.8 g of Ni(NO 3 ) 2 ⁇ 6H 2 O was changed to 12.24 g of Fe(NO 3 ) 3 ⁇ 9H 2 O. The performance was evaluated and the results are shown in Table 1.
  • Example 1 The same experimental conditions as in Example 1 were employed except that the amounts of Ni(NO 3 ) 2 ⁇ 6H 2 O were changed to 4.4 g and 17.6 g, respectively. The performance was evaluated and the results are shown in Table 1.
  • Example 1 The same experimental conditions as in Example 1 were employed except that the amount of Ni-USY was 85 g, the amount of pseudoboehmite was 22.5 g, and the weight of molecular sieve was 85%, and the performance was evaluated. The results are shown in Table 1.
  • Example 1 The same experimental conditions as in Example 1 were employed except that the amount of Ni-USY was 50 g, the amount of pseudoboehmite was 75.0 g, and the molecular sieve weight content was 50%, and the performance was evaluated. The results are shown in Table 1.
  • Example 1 The same experimental conditions as in Example 1 were employed except that the amount of Ni-USY was 30 g, the amount of pseudoboehmite was 105.0 g, and the weight of molecular sieve was 30%, and the performance was evaluated. The results are shown in Table 1.
  • Example 1 The same experimental conditions as in Example 1 were employed except that in the catalyst molding process, 45.0 g of pseudoboehmite was changed to 100 g of a silica sol having a SiO 2 concentration of 30%, wherein the molecular sieve weight content was 70%. The content of the carrier was 30%, and the properties were evaluated. The results are shown in Table 1.
  • Example 1 The same experimental conditions as in Example 1 were employed except that in the catalyst molding process, 45.0 g of pseudoboehmite was changed to 30 g of ⁇ -Al 2 O 3 , wherein the molecular sieve weight content was 70%, and the carrier The content was 30%, and the performance was evaluated. The results are shown in Table 1.
  • the commercially available sulfonic acid resin was acid-impregnated and dried, and 10 g of the catalyst was weighed into a fixed-bed reactor having an inner diameter of 10 mm, and the molar ratio of ethylene glycol monomethyl ether to isobutylene was 1.2/1, and the reaction temperature was used.
  • the reaction results are shown in Table 1 at 60 ° C, the reaction pressure was 0.7 MPa, and the mass space velocity was 1.0 h -1 .
  • Example 1 The same experimental conditions as in Example 1 were employed except that a molecular sieve was used as a zeolite beta having a SiO 2 /Al 2 O 3 molar ratio of 37. The performance was evaluated and the results are shown in Table 1.
  • Example 1 The same experimental conditions as in Example 1 were employed except that the molecular sieve was a ZSM-5 zeolite having a SiO 2 /Al 2 O 3 molar ratio of 40. The performance was evaluated and the results are shown in Table 1.
  • Example 2 The same experimental conditions as in Example 1 were employed except that the reaction pressure was changed to 0.1, 1.0, 1.5, 2.0 MPa, and the properties were evaluated. The results are shown in Table 2.
  • Example 2 The same catalyst and experimental conditions as in Example 1 were employed except that the reaction temperature was changed to 55 ° C, 65 ° C, 70 ° C, and 75 ° C. The experimental results are shown in Table 2.
  • Example 2 The same catalyst and experimental conditions as in Example 1 were employed except that the molar ratio of ethylene glycol monomethyl ether to isobutylene was changed to 1.5:1, 1:1. The experimental results are shown in Table 2.
  • Example 2 The same catalyst and experimental conditions as in Example 1 were employed except that the molar ratio of ethylene glycol monomethyl ether to isobutylene was changed to 1:1.5, 1:2, 1:3. The experimental results are shown in Table 2.
  • Example 2 The same catalyst and experimental conditions as in Example 1 were used except that the feed mass space velocity was changed to 0.5 h -1 , 2.0 h -1 , 3.0 h -1 , 4.0 h -1 .
  • the experimental results are shown in Table 2.
  • Example 28 After the end of Example 28, the ethylene glycol monomethyl ether and isobutylene feeds were stopped, the catalyst bed was purged with 50 ml/min of nitrogen for 30 minutes, and then air was introduced at a rate of 50 ml/min at 8 ° C/min.
  • the catalyst system of Example 28 was regenerated by increasing the temperature from 220 ° C to 500 ° C and then maintaining at 500 ° C for 18 hours. After the end of regeneration, the catalyst bed temperature was lowered to 50 °C.

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Abstract

A catalyst for preparing methoxy ethyl tert-butyl ether by the reaction of ethylene glycol monomethyl ether and isobutylene, comprising the following components in weight percent: a) 40-95 weight% of zeolite molecular sieve modified with a metal and/or an oxide thereof, having a molar ratio of SiO2/Al2O3 of 2-200, the content of the metal and/or the oxide thereof being 0.01-5.0 weight% based on the total weight of the catalyst, the metal being selected from at least one of Ni and Zn; and b) 5-60 weight% of a support, the sum of the components adding up to 100 weight%. A preparation method for the catalyst, use of the catalyst, and a method for preparing methoxy ethyl tert-butyl ether by the reaction of ethylene glycol monomethyl ether and isobutylene in the presence of the catalyst.

Description

用于使乙二醇单甲醚与异丁烯反应制备甲氧基乙基叔丁基醚的催化剂及其制备方法和用途Catalyst for preparing methoxyethyl tert-butyl ether by reacting ethylene glycol monomethyl ether with isobutylene, preparation method and use thereof 技术领域Technical field
本发明涉及一种用于使乙二醇单甲醚与异丁烯反应制备甲氧基乙基叔丁基醚的催化剂及其制备方法和用途，以及在所述催化剂存在下使乙二醇单甲醚与异丁烯反应制备甲氧基乙基叔丁基醚的方法。The present invention relates to a catalyst for reacting ethylene glycol monomethyl ether with isobutylene to prepare methoxyethyl tert-butyl ether, a preparation method and use thereof, and ethylene glycol monomethyl ether in the presence of the catalyst A process for preparing methoxyethyl tert-butyl ether by reaction with isobutylene.
背景技术Background technique
甲氧基乙基叔丁基醚(简称TBME)是一种良好的溶剂，能够与多种有机化合物混溶。另外，由于具有较好的溶解性和稳定性，且十六烷值较高，可以作为柴油添加剂，减少炭烟排放。TBME具有较低的凝点，也可以作为航空柴油的抗冻剂。虽然目前世界上TBME的应用范围不是太广，国内也还没有生产和销售例，但是TBME的合成及应用研究是一个非常有意义的课题。Methoxyethyl tert-butyl ether (TBME for short) is a good solvent that is miscible with a variety of organic compounds. In addition, due to its good solubility and stability, and high cetane number, it can be used as a diesel additive to reduce soot emissions. TBME has a low freezing point and can also be used as an antifreeze for aviation diesel. Although the scope of application of TBME in the world is not too wide, there are no production and sales examples in China, but the synthesis and application research of TBME is a very significant topic.
目前有关TBME合成路线的介绍很少，一般认为从乙二醇单甲醚与异丁烯出发进行醚化最为经济可行。At present, there are few introductions about the TBME synthesis route. It is generally considered that it is most economically feasible to carry out etherification from ethylene glycol monomethyl ether and isobutylene.
GB1587272A中介绍了一种使用离子交换的磺酸树脂催化剂，在间歇釜反应器中由乙二醇单甲醚和异丁烯反应制备TBME的方法，将催化剂和乙二醇单甲醚装入反应釜中，在85℃和2.5巴下，通入异丁烯进行反应，乙二醇单甲醚和异丁烯的重量比为4:3，最终异丁烯的转化率为70％。该文献对于产物的选择性和催化剂的重复使用情况都没有作说明。GB1587272A describes a method for preparing TBME by reacting ethylene glycol monomethyl ether and isobutylene in a batch reactor using a sulfonic acid resin catalyst. The catalyst and ethylene glycol monomethyl ether are charged into the reaction vessel. The reaction was carried out by introducing isobutylene at 85 ° C and 2.5 bar. The weight ratio of ethylene glycol monomethyl ether to isobutylene was 4:3, and the final conversion of isobutylene was 70%. This document does not describe the selectivity of the product and the repeated use of the catalyst.
EP0055045A1认为，用磺酸树脂作为催化剂进行异丁烯与醇类的醚化反应，存在催化剂的热稳定性差的缺陷，并开发了一种Nu-2分子筛类的催化剂用于异丁烯与醇类的醚化反应，该文献中提到的醇包含乙二醇单甲醚，在Nu-2催化剂作用下，0.21mol的异丁烯和0.25mol的乙二醇单甲醚在间歇釜反应器中，于90℃和自生压力下反应，结果是异丁烯的转化率为42.3％，TBME的选择性为96.5％，该文献没有报道催化剂的重复使用情况。EP0055045A1 considers the use of a sulfonic acid resin as a catalyst for the etherification reaction of isobutylene with an alcohol, which has the disadvantage of poor thermal stability of the catalyst, and has developed a catalyst of Nu-2 molecular sieve for the etherification reaction of isobutylene with an alcohol. The alcohol mentioned in the literature comprises ethylene glycol monomethyl ether, under the action of a Nu-2 catalyst, 0.21 mol of isobutylene and 0.25 mol of ethylene glycol monomethyl ether in a batch reactor at 90 ° C and spontaneously The reaction under pressure resulted in a conversion of isobutylene of 42.3% and a selectivity of TBME of 96.5%. This document does not report repeated use of the catalyst.
GB1587272A所用的树脂催化剂的活性比较高，但是树脂催化剂热稳 定性差的缺陷很明显，EP0055045A1虽然采用分子筛取代磺酸树脂催化剂，催化剂的热稳定性得到改善，但是异丁烯的转化率比较低。The resin catalyst used in GB1587272A has relatively high activity, but the defect of poor thermal stability of the resin catalyst is obvious. Although EP0055045A1 uses molecular sieve instead of sulfonic acid resin catalyst, the thermal stability of the catalyst is improved, but the conversion rate of isobutylene is relatively low.
基于现有技术的现状，亟需开发出一种能够工业化合成TBME的方法，其使用环境友好，稳定性好的固体酸催化剂，能够高效地将乙二醇单甲醚与异丁烯转化为TBME。Based on the current state of the art, there is an urgent need to develop a method for industrially synthesizing TBME using an environmentally friendly, stable solid acid catalyst capable of efficiently converting ethylene glycol monomethyl ether and isobutylene into TBME.
发明内容Summary of the invention
本发明为了克服现有技术中存在的上述问题，提供一种用于乙二醇单甲醚和异丁烯反应制备TBME的新型催化剂，该催化剂环境友好，具有高的异丁烯转化率和TBME选择性，好的稳定性和再生性能。In order to overcome the above problems existing in the prior art, the present invention provides a novel catalyst for preparing TBME by reacting ethylene glycol monomethyl ether with isobutylene, which is environmentally friendly, has high isobutene conversion and TBME selectivity, and is good. Stability and regeneration performance.
本发明采用的技术方案如下：一种用于由乙二醇单甲醚和异丁烯反应制备TBME的催化剂，以重量百分比计包含以下组分:The technical scheme adopted by the present invention is as follows: A catalyst for preparing TBME by reacting ethylene glycol monomethyl ether with isobutylene, and comprises the following components in weight percentage:
a)40-95重量％的SiO 2/Al 2O 3摩尔比为2-200的金属和/或其氧化物改性的沸石分子筛，其中金属和/或其氧化物的含量基于催化剂的总重量为0.01-5.0重量％，所述金属选自Ni和Zn中的至少一种；和 a) 40 to 95% by weight of a metal having a molar ratio of SiO 2 /Al 2 O 3 of from 2 to 200 and/or its oxide-modified zeolite molecular sieve, wherein the content of the metal and/or its oxide is based on the total weight of the catalyst From 0.01 to 5.0% by weight, the metal is selected from at least one of Ni and Zn;
b)5-60重量％的载体；b) 5 to 60% by weight of the carrier;
其中各组分的总和加起来为100重量％。The sum of the components is added up to 100% by weight.
本发明的另一目的是提供一种制备本发明催化剂的方法，该方法包括以下步骤：Another object of the present invention is to provide a process for the preparation of the catalyst of the present invention which comprises the steps of:
(1)提供SiO 2/Al 2O 3摩尔比为2-200的H型沸石分子筛； (1) providing an H-type zeolite molecular sieve having a SiO 2 /Al 2 O 3 molar ratio of 2 to 200 ;
(2)将水溶性金属盐的水溶液与步骤(1)的H型沸石分子筛接触，然后过滤、清洗、干燥和焙烧，得到改性的沸石分子筛，其中所述金属选自Ni和Zn中的至少一种；和(2) contacting an aqueous solution of a water-soluble metal salt with the H-type zeolite molecular sieve of the step (1), followed by filtration, washing, drying and calcination to obtain a modified zeolite molecular sieve, wherein the metal is selected from at least Ni and Zn. One; and
(3)将步骤(2)得到的改性的沸石分子筛与载体或载体前体、成型助剂、酸和水捏合，然后成型、干燥、焙烧、破碎和筛分，得到固体颗粒，(3) kneading the modified zeolite molecular sieve obtained in the step (2) with a carrier or a carrier precursor, a molding aid, an acid and water, followed by molding, drying, calcining, crushing and sieving to obtain solid particles.
其中各组分的用量使得以催化剂的总重量计，该催化剂包含以下组分：The amount of each component is such that, based on the total weight of the catalyst, the catalyst comprises the following components:
a)40-95重量％的SiO 2/Al 2O 3摩尔比为2-200的金属和/或其氧化物改性的沸石分子筛，其中金属和/或其氧化物的含量基于催化剂的总重量为 0.01-5.0重量％，所述金属选自Ni和Zn中的至少一种；和 a) 40 to 95% by weight of a metal having a molar ratio of SiO 2 /Al 2 O 3 of from 2 to 200 and/or its oxide-modified zeolite molecular sieve, wherein the content of the metal and/or its oxide is based on the total weight of the catalyst From 0.01 to 5.0% by weight, the metal is selected from at least one of Ni and Zn;
b)5-60重量％的载体；b) 5 to 60% by weight of the carrier;
其中各组分的总和加起来为100重量％。The sum of the components is added up to 100% by weight.
本发明的再一目的是提供一种制备甲氧基乙基叔丁基醚的方法，该方法包括：在醚化条件下，使乙二醇单甲醚和异丁烯与本发明催化剂接触。A further object of the present invention is to provide a process for the preparation of methoxyethyl tert-butyl ether which comprises contacting ethylene glycol monomethyl ether and isobutylene with a catalyst of the invention under etherification conditions.
本发明的又一目的是提供本发明催化剂在制备甲氧基乙基叔丁基醚中的用途。A further object of the invention is to provide the use of the catalyst of the invention in the preparation of methoxyethyl tert-butyl ether.
具体实施方式Detailed ways
本发明一方面提供了一种用于由乙二醇单甲醚和异丁烯反应制备TBME的催化剂，以重量百分比计包含以下组分:In one aspect, the invention provides a catalyst for the preparation of TBME from the reaction of ethylene glycol monomethyl ether with isobutylene, comprising, by weight percent, the following components:
a)40-95重量％的SiO 2/Al 2O 3摩尔比为2-200的金属和/或其氧化物改性的沸石分子筛，其中金属和/或其氧化物的含量基于催化剂的总重量为0.01-5.0重量％，所述金属选自Ni和Zn中的至少一种；和 a) 40 to 95% by weight of a metal having a molar ratio of SiO 2 /Al 2 O 3 of from 2 to 200 and/or its oxide-modified zeolite molecular sieve, wherein the content of the metal and/or its oxide is based on the total weight of the catalyst From 0.01 to 5.0% by weight, the metal is selected from at least one of Ni and Zn;
b)5-60重量％的载体；b) 5 to 60% by weight of the carrier;
其中各组分的总和加起来为100重量％。The sum of the components is added up to 100% by weight.
本发明催化剂包含优选55-90重量％，更优选65-88重量％的组分a)。The catalyst according to the invention comprises preferably from 55 to 90% by weight, more preferably from 65 to 88% by weight, of component a).
本发明催化剂包含优选10-45重量％，更优选12-35重量％的组分b)。The catalyst according to the invention comprises preferably from 10 to 45% by weight, more preferably from 12 to 35% by weight, of component b).
本发明催化剂中所用沸石分子筛的SiO 2/Al 2O 3摩尔比优选为3-160，更优选5-120。 The zeolitic molecular sieve used in the catalyst of the present invention preferably has a SiO 2 /Al 2 O 3 molar ratio of from 3 to 160, more preferably from 5 to 120.
本发明催化剂中金属和/或其氧化物的含量基于催化剂的总重量优选为0.1-3.0重量％。The content of the metal and/or its oxide in the catalyst of the invention is preferably from 0.1 to 3.0% by weight, based on the total weight of the catalyst.
本发明催化剂中所用沸石分子筛基于本领域技术人员所公知的沸石分子筛，例如沸石分子筛选自USY沸石分子筛、β沸石分子筛和丝光沸石分子筛中的一种或多种，更进一步优选为USY沸石分子筛和/或β沸石分子筛，尤其优选为USY沸石分子筛。The zeolite molecular sieve used in the catalyst of the present invention is based on zeolite molecular sieves well known to those skilled in the art, for example, zeolite molecules are screened from one or more of USY zeolite molecular sieves, beta zeolite molecular sieves and mordenite molecular sieves, still more preferably USY zeolite molecular sieves and / or beta zeolite molecular sieves, particularly preferably USY zeolite molecular sieves.
本发明对沸石分子筛的来源没有特别要求，可以通过市购得到，也可以通过现有技术合成沸石分子筛的方法得到。The present invention has no particular requirement for the source of the zeolite molecular sieve, and is commercially available or can be obtained by a method for synthesizing a zeolite molecular sieve by the prior art.
在本发明的一个优选实施方式中，所述沸石分子筛为USY沸石分子筛。从TBME的选择性进行考虑，本发明组分a)中所述金属优选为Ni。In a preferred embodiment of the invention, the zeolite molecular sieve is a USY zeolite molecular sieve. In view of the selectivity of TBME, the metal in component a) of the invention is preferably Ni.
本发明对所用载体的种类没有特别的限定，可以根据实际需要进行选择。例如载体可以选自γ-Al 2O 3和二氧化硅中的一种或多种。 The type of the carrier to be used in the present invention is not particularly limited, and may be selected according to actual needs. For example, the carrier may be selected from one or more of γ-Al 2 O 3 and silica.
本发明另一方面提供了一种制备本发明催化剂的方法，该方法包括:Another aspect of the invention provides a method of preparing a catalyst of the invention, the method comprising:
(1)提供SiO 2/Al 2O 3摩尔比为2-200的H型沸石分子筛； (1) providing an H-type zeolite molecular sieve having a SiO 2 /Al 2 O 3 molar ratio of 2 to 200 ;
(2)将水溶性金属盐的水溶液与步骤(1)的H型沸石分子筛接触，然后过滤、清洗、干燥和焙烧，得到改性的沸石分子筛，其中所述金属选自Ni和Zn中的至少一种；和(2) contacting an aqueous solution of a water-soluble metal salt with the H-type zeolite molecular sieve of the step (1), followed by filtration, washing, drying and calcination to obtain a modified zeolite molecular sieve, wherein the metal is selected from at least Ni and Zn. One; and
(3)将步骤(2)得到的改性的沸石分子筛与载体或载体前体、成型助剂、酸和水捏合，然后成型、干燥、焙烧、破碎和筛分，得到固体颗粒，(3) kneading the modified zeolite molecular sieve obtained in the step (2) with a carrier or a carrier precursor, a molding aid, an acid and water, followed by molding, drying, calcining, crushing and sieving to obtain solid particles.
其中各组分的用量使得以催化剂的总重量计，该催化剂包含以下组分：The amount of each component is such that, based on the total weight of the catalyst, the catalyst comprises the following components:
a)40-95重量％的SiO 2/Al 2O 3摩尔比为2-200的金属和/或其氧化物改性的沸石分子筛，其中金属和/或其氧化物的含量基于催化剂的总重量为0.01-5.0重量％，所述金属选自Ni和Zn中的至少一种；和 a) 40 to 95% by weight of a metal having a molar ratio of SiO 2 /Al 2 O 3 of from 2 to 200 and/or its oxide-modified zeolite molecular sieve, wherein the content of the metal and/or its oxide is based on the total weight of the catalyst From 0.01 to 5.0% by weight, the metal is selected from at least one of Ni and Zn;
b)5-60重量％的载体；b) 5 to 60% by weight of the carrier;
其中各组分的总和加起来为100重量％。The sum of the components is added up to 100% by weight.
根据本发明，在步骤(2)中所用水溶性金属盐的种类可以在较大的范围内进行选择。例如，所述水溶性金属盐可以选自Ni和Zn的水溶性盐中的至少一种；优选所述水溶性金属盐选自Ni的水溶性盐中的至少一种。具体地，所述水溶性金属盐可以选自Ni和Zn的硝酸盐、碳酸盐、磷酸盐、亚磷酸盐和盐酸盐中的至少一种，优选选自Ni的硝酸盐、碳酸盐、磷酸盐、亚磷酸盐和盐酸盐中的至少一种。According to the present invention, the kind of the water-soluble metal salt used in the step (2) can be selected within a wide range. For example, the water-soluble metal salt may be at least one selected from the group consisting of water-soluble salts of Ni and Zn; preferably, the water-soluble metal salt is at least one selected from the group consisting of water-soluble salts of Ni. Specifically, the water-soluble metal salt may be at least one selected from the group consisting of nitrates, carbonates, phosphates, phosphites, and hydrochlorides of Ni and Zn, preferably selected from the group consisting of nitrates and carbonates of Ni. At least one of a phosphate, a phosphite, and a hydrochloride.
本发明对步骤(2)中将水溶性金属盐的水溶液与步骤(1)的H型沸石分子筛接触的条件没有特别要求，一般地，接触的条件可以包括：接触的温度可以为50-150℃，优选55-120℃；接触的时间可以为2-10小时，优选 3-8小时。The present invention has no particular requirement for the conditions of contacting the aqueous solution of the water-soluble metal salt with the H-type zeolite molecular sieve of the step (1) in the step (2). Generally, the contact conditions may include: the contact temperature may be 50-150 ° C. Preferably, the temperature is from 55 to 120 ° C; the contact time may be from 2 to 10 hours, preferably from 3 to 8 hours.
本发明对步骤(2)中的其他操作没有特别要求，可以使用本领域公知的方法进行。The present invention has no particular requirements for other operations in step (2) and can be carried out using methods well known in the art.
本发明对步骤(3)中捏合的条件没有特别要求，一般地，捏合的条件可以包括：捏合的温度可以为20-50℃，优选25-45℃；捏合的时间可以为20-90分钟，优选25-45分钟。The present invention has no particular requirement for the conditions of kneading in the step (3). Generally, the kneading conditions may include: the kneading temperature may be 20-50 ° C, preferably 25-45 ° C; the kneading time may be 20-90 minutes, It is preferably 25-45 minutes.
本发明还包括步骤(3)中捏合后的成型、干燥和焙烧步骤。成型的方法、干燥的方法和焙烧的方法可以使用本领域公知的方法进行。The present invention also includes the steps of forming, drying and calcining after kneading in the step (3). The method of molding, the method of drying, and the method of firing can be carried out using methods well known in the art.
本发明步骤(3)中干燥可以为常规的制备H型沸石分子筛的干燥条件，具体地，干燥的温度可以为50-250℃，优选100-200℃；干燥的时间可以为6-120小时，优选10-96小时。The drying in the step (3) of the present invention may be a conventional drying condition for preparing the H-type zeolite molecular sieve. Specifically, the drying temperature may be 50-250 ° C, preferably 100-200 ° C; and the drying time may be 6-120 hours. It is preferably 10-96 hours.
本发明步骤(3)中焙烧可以为常规的制备H型沸石分子筛的焙烧条件。例如，焙烧的温度可以为500-750℃；优选为520-650℃；焙烧的时间可以为1-10小时，优选为3-8小时；焙烧的气氛可以为空气或惰性气体，例如N 2。 The calcination in the step (3) of the present invention may be a conventional calcination condition for preparing a zeolite H molecular sieve. For example, the calcination temperature may be 500 to 750 ° C; preferably 520 to 650 ° C; the calcination time may be 1 to 10 hours, preferably 3 to 8 hours; and the calcination atmosphere may be air or an inert gas such as N 2 .
本发明对步骤(3)中所使用的酸没有特别限制，包括无机酸(如硝酸、盐酸、硫酸等)或有机酸(甲酸、乙酸、丙酸、草酸等)中的至少一种。成型助剂可以选自田箐粉、聚乙烯醇和聚乙二醇中的至少一种。The acid used in the step (3) is not particularly limited, and includes at least one of a mineral acid (e.g., nitric acid, hydrochloric acid, sulfuric acid, etc.) or an organic acid (formic acid, acetic acid, propionic acid, oxalic acid, etc.). The molding aid may be at least one selected from the group consisting of glutinous rice flour, polyvinyl alcohol, and polyethylene glycol.
本发明对步骤(3)中的破碎和筛分步骤没有特别限制，可使用本领域公知的任何方法。The present invention is not particularly limited to the crushing and sieving step in the step (3), and any method known in the art can be used.
在本发明的制备方法中，H型沸石分子筛的种类和用量、SiO 2/Al 2O 3摩尔比、载体的种类和用量如上所述，在此不再赘述。对于载体前体，可以选自铝溶胶、拟薄水铝石、硅溶胶和粘土中的至少一种。 In the preparation method of the present invention, the kind and amount of the H-type zeolite molecular sieve, the SiO 2 /Al 2 O 3 molar ratio, the kind and amount of the carrier are as described above, and will not be described herein. For the carrier precursor, at least one selected from the group consisting of aluminum sol, pseudoboehmite, silica sol, and clay may be selected.
本发明再一方面提供了一种制备甲氧基乙基叔丁基醚的方法，该方法包括：使乙二醇单甲醚和异丁烯与本发明催化剂接触。In a further aspect of the invention there is provided a process for the preparation of methoxyethyl tert-butyl ether which comprises contacting ethylene glycol monomethyl ether and isobutylene with a catalyst of the invention.
根据本发明，对于乙二醇单甲醚与异丁烯的摩尔比没有特别限制，例如，所述摩尔比可以为0.7-10:1，优选为0.8-5:1，更优选为0.9-2:1。According to the present invention, the molar ratio of ethylene glycol monomethyl ether to isobutylene is not particularly limited, and for example, the molar ratio may be from 0.7 to 10:1, preferably from 0.8 to 5:1, more preferably from 0.9 to 2:1. .
根据本发明，对于乙二醇单甲醚和异丁烯与催化剂接触的条件没有特别限制，例如所述接触的条件可以包括：接触的温度为30-100℃，和/或接 触的压力为0.01-5.0MPa，和/或质量空速为0.1-10h -1。从反应转化率与TBME的角度进行考虑，优选接触的温度为50-70℃，和/或接触的压力为0.1-3.0MPa，和/或质量空速为0.1-5h -1。 According to the present invention, the conditions for contacting ethylene glycol monomethyl ether and isobutylene with a catalyst are not particularly limited, and for example, the conditions of the contact may include: a contact temperature of 30 to 100 ° C, and/or a contact pressure of 0.01 to 5.0. The MPa, and/or mass space velocity is 0.1-10 h -1 . From the viewpoint of reaction conversion ratio and TBME, it is preferred that the contact temperature is 50-70 ° C, and/or the contact pressure is 0.1-3.0 MPa, and/or the mass space velocity is 0.1-5 h -1 .
在本发明的制备甲氧基乙基叔丁基醚的方法中，对接触进行的反应器的形式没有特别的限定，所述反应器可以为固定床反应器、浆态床反应器、间歇釜反应器、流化床反应器、移动床反应器和独石反应器中的至少一种的组合。在本发明中，所述独石反应器是指使用泡沫独石整体型催化剂的反应器，优选所述反应器为固定床。In the method for producing methoxyethyl tert-butyl ether of the present invention, the form of the reactor to be contacted is not particularly limited, and the reactor may be a fixed bed reactor, a slurry bed reactor, or a batch reactor. A combination of at least one of a reactor, a fluidized bed reactor, a moving bed reactor, and a monolithic reactor. In the present invention, the monolithic reactor refers to a reactor using a monolithic catalyst of a monolith, and preferably the reactor is a fixed bed.
本发明又一方面提供了本发明催化剂在制备甲氧基乙基叔丁基醚中的用途。A further aspect of the invention provides the use of a catalyst of the invention in the preparation of methoxyethyl tert-butyl ether.
下面借助实施例详细描述本发明，但本发明的范围并不限于此。The invention is described in detail below with the aid of examples, but the scope of the invention is not limited thereto.
实施例Example
以下实施例中，采用气相色谱进行体系中各组成的分析，通过校正归一法进行定量，均可参照现有技术进行，在此基础上计算反应物的转化率、产物的收率和选择性等评价指标。In the following examples, the analysis of each component in the system by gas chromatography and the quantification by the calibration normalization method can be carried out by referring to the prior art, on the basis of which the conversion rate of the reactants, the yield and selectivity of the product are calculated. And other evaluation indicators.
本发明中，异丁烯的转化率计算公式如下:In the present invention, the conversion formula of isobutylene is calculated as follows:
Figure PCTCN2018091298-appb-000001
Figure PCTCN2018091298-appb-000001
各产物的选择性:Selectivity of each product:
Figure PCTCN2018091298-appb-000002
Figure PCTCN2018091298-appb-000002
其中，X为异丁烯转化率；S为选择性；m为组分的质量；n为产物中各组分的质量。Wherein X is the conversion of isobutylene; S is the selectivity; m is the mass of the component; and n is the mass of each component in the product.
实施例1Example 1
将100克SiO 2/Al 2O 3摩尔比为7的铵型USY沸石分子筛(产品型号HSZ-341NHA、生产商TOSOH)在550℃下焙烧5小时，得到H型USY沸石分子筛。 100 g of an ammonium type USY zeolite molecular sieve (product type HSZ-341NHA, manufacturer TOSOH) having a molar ratio of SiO 2 /Al 2 O 3 of 7 was calcined at 550 ° C for 5 hours to obtain a H-type USY zeolite molecular sieve.
称取8.8g的Ni(NO 3) 2·6H 2O溶于300ml去离子水中，加入100g SiO 2/Al 2O 3摩尔比为7的上述制备得到的H型USY沸石分子筛，在60℃下搅拌4小时，然后过滤，去离子水清洗，再次过滤，置于120℃的烘箱中12小时，于550℃马弗炉中焙烧5小时，得到改性的Ni-USY沸石分子筛。 Weigh 8.8g of Ni(NO 3 ) 2 ·6H 2 O dissolved in 300ml of deionized water, and add 100g of SiO 2 /Al 2 O 3 molar ratio of the above prepared H type USY zeolite molecular sieve at 60 ° C After stirring for 4 hours, it was filtered, washed with deionized water, filtered again, placed in an oven at 120 ° C for 12 hours, and calcined in a muffle furnace at 550 ° C for 5 hours to obtain a modified Ni-USY zeolite molecular sieve.
称取70g制得的Ni-USY沸石分子筛，45g拟薄水铝石(Al 2O 3含量66.7％)，5g田箐粉，60g H 2O，加入5g浓硝酸在25℃下捏合30分钟，用直径为3.0毫米的模具挤条成型，晾干，置于120℃的烘箱中12小时，于550℃马弗炉中焙烧5小时。然后破碎，筛分，得到粒径为1mm的催化剂体系。 70 g of the obtained Ni-USY zeolite molecular sieve, 45 g of pseudoboehmite (Al 2 O 3 content 66.7%), 5 g of glutinous rice flour, 60 g of H 2 O, and 5 g of concentrated nitric acid were kneaded at 25 ° C for 30 minutes. The mixture was extruded with a die having a diameter of 3.0 mm, dried, placed in an oven at 120 ° C for 12 hours, and fired in a muffle furnace at 550 ° C for 5 hours. Then, it was crushed and sieved to obtain a catalyst system having a particle diameter of 1 mm.
将上述制备的催化剂10g放入内径为10毫米的固定床反应器内，采用乙二醇单甲醚与异丁烯的摩尔比为1.2/1，反应温度为60℃，反应压力为0.7MPa，质量空速为1.0h -1的条件下，异丁烯的转化率为96％，TMBE的选择性为99.8％。 10 g of the catalyst prepared above was placed in a fixed bed reactor having an inner diameter of 10 mm, using a molar ratio of ethylene glycol monomethyl ether to isobutylene of 1.2/1, a reaction temperature of 60 ° C, a reaction pressure of 0.7 MPa, and an empty mass. At a rate of 1.0 h -1 , the conversion of isobutylene was 96% and the selectivity of TMBE was 99.8%.
对比实施例1Comparative Example 1
采用与实施例1相同的实验条件，所不同的是不添加Ni(NO 3) 2·6H 2O。并考评其性能，结果列于表1。 The same experimental conditions as in Example 1 were employed except that Ni(NO 3 ) 2 ·6H 2 O was not added. The performance was evaluated and the results are shown in Table 1.
实施例2-4Example 2-4
采用与实施例1相同的实验条件，所不同的是改变USY沸石分子筛的SiO 2/Al 2O 3摩尔比分别为30、80和110，并考评其性能，结果列于表1。 The same experimental conditions as in Example 1 were employed except that the SiO 2 /Al 2 O 3 molar ratios of the USY zeolite molecular sieves were changed to 30, 80 and 110, respectively, and their properties were evaluated. The results are shown in Table 1.
实施例5Example 5
采用与实施例1相同的实验条件，所不同的是将8.8g Ni(NO 3) 2·6H 2O改为8.88g Zn(NO 3) 2·6H 2O。并考评其性能，结果列于表1。 The same experimental conditions as in Example 1 were employed except that 8.8 g of Ni(NO 3 ) 2 ·6H 2 O was changed to 8.88 g of Zn(NO 3 ) 2 ·6H 2 O. The performance was evaluated and the results are shown in Table 1.
对比实施例2Comparative Example 2
采用与实施例1相同的实验条件，所不同的是将8.8g Ni(NO 3) 2·6H 2O改为7.32g Cu(NO 3) 2·3H 2O。并考评其性能，结果列于表1。 The same experimental conditions as in Example 1 were employed except that 8.8 g of Ni(NO 3 ) 2 ·6H 2 O was changed to 7.32 g of Cu(NO 3 ) 2 ·3H 2 O. The performance was evaluated and the results are shown in Table 1.
对比实施例3Comparative Example 3
采用与实施例1相同的实验条件，所不同的是将8.8g Ni(NO 3) 2·6H 2O改为12.24g Fe(NO 3) 3·9H 2O。并考评其性能，结果列于表1。 The same experimental conditions as in Example 1 were employed except that 8.8 g of Ni(NO 3 ) 2 ·6H 2 O was changed to 12.24 g of Fe(NO 3 ) 3 ·9H 2 O. The performance was evaluated and the results are shown in Table 1.
实施例6-7Example 6-7
采用与实施例1相同的实验条件，所不同的是将改变Ni(NO 3) 2·6H 2O的量，分别为4.4g和17.6g。并考评其性能，结果列于表1。 The same experimental conditions as in Example 1 were employed except that the amounts of Ni(NO 3 ) 2 ·6H 2 O were changed to 4.4 g and 17.6 g, respectively. The performance was evaluated and the results are shown in Table 1.
实施例8Example 8
采用与实施例1相同的实验条件，所不同的是在催化剂成型过程中，Ni-USY的量为85g，拟薄水铝石的量为22.5g，分子筛重量含量为85％，评其性能，结果列于表1。The same experimental conditions as in Example 1 were employed except that the amount of Ni-USY was 85 g, the amount of pseudoboehmite was 22.5 g, and the weight of molecular sieve was 85%, and the performance was evaluated. The results are shown in Table 1.
实施例9Example 9
采用与实施例1相同的实验条件，所不同的是在催化剂成型过程中，Ni-USY的量为50g，拟薄水铝石的量为75.0g，分子筛重量含量为50％，评其性能，结果列于表1。The same experimental conditions as in Example 1 were employed except that the amount of Ni-USY was 50 g, the amount of pseudoboehmite was 75.0 g, and the molecular sieve weight content was 50%, and the performance was evaluated. The results are shown in Table 1.
对比实施例4Comparative Example 4
采用与实施例1相同的实验条件，所不同的是在催化剂成型过程中，Ni-USY的量为30g，拟薄水铝石的量为105.0g，分子筛重量含量为30％，评其性能，结果列于表1。The same experimental conditions as in Example 1 were employed except that the amount of Ni-USY was 30 g, the amount of pseudoboehmite was 105.0 g, and the weight of molecular sieve was 30%, and the performance was evaluated. The results are shown in Table 1.
实施例10Example 10
采用与实施例1相同的实验条件，所不同的是在催化剂成型过程中，将45.0g的拟薄水铝石改为30g粘土，其中分子筛重量含量为70％，载体的含量为30％，评其性能，结果列于表1。The same experimental conditions as in Example 1 were used except that 45.0 g of pseudoboehmite was changed to 30 g of clay during the molding of the catalyst, wherein the molecular sieve weight content was 70% and the carrier content was 30%. Its performance, the results are listed in Table 1.
实施例11Example 11
采用与实施例1相同的实验条件，所不同的是在催化剂成型过程中，将45.0g的拟薄水铝石改为100g的SiO 2浓度为30％的硅溶胶，其中分子筛重量含量为70％，载体的含量为30％，评其性能，结果列于表1。 The same experimental conditions as in Example 1 were employed except that in the catalyst molding process, 45.0 g of pseudoboehmite was changed to 100 g of a silica sol having a SiO 2 concentration of 30%, wherein the molecular sieve weight content was 70%. The content of the carrier was 30%, and the properties were evaluated. The results are shown in Table 1.
实施例12Example 12
采用与实施例1相同的实验条件，所不同的是在催化剂成型过程中，将45.0g的拟薄水铝石改为30g的γ-Al 2O 3，其中分子筛重量含量为70％，载体的含量为30％，评其性能，结果列于表1。 The same experimental conditions as in Example 1 were employed except that in the catalyst molding process, 45.0 g of pseudoboehmite was changed to 30 g of γ-Al 2 O 3 , wherein the molecular sieve weight content was 70%, and the carrier The content was 30%, and the performance was evaluated. The results are shown in Table 1.
对比实施例5Comparative Example 5
将商购的磺酸树脂经过酸浸渍和烘干，称取催化剂10g放入内径为10毫米的固定床反应器内，采用乙二醇单甲醚与异丁烯的摩尔比为1.2/1，反应温度为60℃，反应压力为0.7MPa，质量空速为1.0h -1的条件下，反应结果列于表1。 The commercially available sulfonic acid resin was acid-impregnated and dried, and 10 g of the catalyst was weighed into a fixed-bed reactor having an inner diameter of 10 mm, and the molar ratio of ethylene glycol monomethyl ether to isobutylene was 1.2/1, and the reaction temperature was used. The reaction results are shown in Table 1 at 60 ° C, the reaction pressure was 0.7 MPa, and the mass space velocity was 1.0 h -1 .
实施例13Example 13
采用与实施例1相同的实验条件，所不同的是使用分子筛为SiO 2/Al 2O 3摩尔比为37的β沸石。并考评其性能，结果列于表1。 The same experimental conditions as in Example 1 were employed except that a molecular sieve was used as a zeolite beta having a SiO 2 /Al 2 O 3 molar ratio of 37. The performance was evaluated and the results are shown in Table 1.
对比实施例6Comparative Example 6
采用与实施例1相同的实验条件，所不同的是使用分子筛为SiO 2/Al 2O 3摩尔比为40的ZSM-5沸石。并考评其性能，结果列于表1。 The same experimental conditions as in Example 1 were employed except that the molecular sieve was a ZSM-5 zeolite having a SiO 2 /Al 2 O 3 molar ratio of 40. The performance was evaluated and the results are shown in Table 1.
实施例14-17Example 14-17
采用与实施例1相同的实验条件，所不同的是改变反应压力为0.1，1.0，1.5，2.0MPa，并考评其性能，结果列于表2中。The same experimental conditions as in Example 1 were employed except that the reaction pressure was changed to 0.1, 1.0, 1.5, 2.0 MPa, and the properties were evaluated. The results are shown in Table 2.
实施例18-21Example 18-21
采用与实施例1相同的催化剂和实验条件，所不同的是只是改变反应温 度为55℃，65℃，70℃，75℃。实验结果列于表2中。The same catalyst and experimental conditions as in Example 1 were employed except that the reaction temperature was changed to 55 ° C, 65 ° C, 70 ° C, and 75 ° C. The experimental results are shown in Table 2.
实施例22-23Example 22-23
采用与实施例1相同的催化剂和实验条件，所不同的是只是改变乙二醇单甲醚和异丁烯的摩尔比为1.5:1，1:1。实验结果列于表2中。The same catalyst and experimental conditions as in Example 1 were employed except that the molar ratio of ethylene glycol monomethyl ether to isobutylene was changed to 1.5:1, 1:1. The experimental results are shown in Table 2.
对比实施例7-9Comparative Examples 7-9
采用与实施例1相同的催化剂和实验条件，所不同的是只是改变乙二醇单甲醚和异丁烯的摩尔比为1:1.5，1:2，1:3。实验结果列于表2中。The same catalyst and experimental conditions as in Example 1 were employed except that the molar ratio of ethylene glycol monomethyl ether to isobutylene was changed to 1:1.5, 1:2, 1:3. The experimental results are shown in Table 2.
实施例24-27Example 24-27
采用与实施例1相同的催化剂和实验条件，所不同的是只是改变进料质量空速为0.5h -1，2.0h -1，3.0h -1，4.0h -1。实验结果列于表2中。 The same catalyst and experimental conditions as in Example 1 were used except that the feed mass space velocity was changed to 0.5 h -1 , 2.0 h -1 , 3.0 h -1 , 4.0 h -1 . The experimental results are shown in Table 2.
实施例28Example 28
采用与实施例1相同的实验条件，反应720小时。不同在线时间下异丁烯转化率和TBME选择性的实验结果列于表3中。The reaction was carried out for 720 hours under the same experimental conditions as in Example 1. The experimental results of isobutene conversion and TBME selectivity at different online times are listed in Table 3.
实施例29Example 29
实施例28结束后，停止乙二醇单甲醚和异丁烯进料，用50ml/min的氮气吹扫催化剂床层30分钟，然后再以50ml/min的速度通入空气，以8℃/分钟的速度将温度从220℃升到500℃，然后在500℃下保持18小时，将实施例28中的催化剂体系进行再生。再生结束后，催化剂床层温度降到50℃。After the end of Example 28, the ethylene glycol monomethyl ether and isobutylene feeds were stopped, the catalyst bed was purged with 50 ml/min of nitrogen for 30 minutes, and then air was introduced at a rate of 50 ml/min at 8 ° C/min. The catalyst system of Example 28 was regenerated by increasing the temperature from 220 ° C to 500 ° C and then maintaining at 500 ° C for 18 hours. After the end of regeneration, the catalyst bed temperature was lowered to 50 °C.
将再生后的催化剂体系采用实施例28相同的实验条件，进行催化剂的稳定性实验，实验结果如表3所示。The catalyst system after the regeneration was subjected to the same experimental conditions as in Example 28, and the stability test of the catalyst was carried out. The experimental results are shown in Table 3.
表1.催化剂组成对醚化反应的影响Table 1. Effect of catalyst composition on etherification reaction
Figure PCTCN2018091298-appb-000003
Figure PCTCN2018091298-appb-000003
Figure PCTCN2018091298-appb-000004
Figure PCTCN2018091298-appb-000004
表2.反应条件对醚化反应的影响Table 2. Effect of reaction conditions on etherification reaction
Figure PCTCN2018091298-appb-000005
Figure PCTCN2018091298-appb-000005
Figure PCTCN2018091298-appb-000006
Figure PCTCN2018091298-appb-000006

Claims (11)

  1. 一种用于由乙二醇单甲醚和异丁烯反应制备甲氧基乙基叔丁基醚的催化剂，以重量百分比计包含以下组分:A catalyst for the preparation of methoxyethyl tert-butyl ether from the reaction of ethylene glycol monomethyl ether with isobutylene, comprising, by weight percent, the following components:
    a)40-95重量％，优选55-90重量％，更优选65-88重量％的SiO 2/Al 2O 3摩尔比为2-200，优选3-160，更优选5-120的金属和/或其氧化物改性的沸石分子筛，其中金属和/或其氧化物的含量基于催化剂的总重量为0.01-5.0重量％，优选0.1-3.0重量％，所述金属选自Ni和Zn中的至少一种；和 a) 40 to 95% by weight, preferably 55 to 90% by weight, more preferably 65 to 88% by weight, of a metal having a SiO 2 /Al 2 O 3 molar ratio of from 2 to 200 , preferably from 3 to 160, more preferably from 5 to 120 / or an oxide-modified zeolite molecular sieve thereof, wherein the content of the metal and/or its oxide is from 0.01 to 5.0% by weight, preferably from 0.1 to 3.0% by weight, based on the total weight of the catalyst, the metal being selected from the group consisting of Ni and Zn At least one; and
    b)5-60重量％，优选10-45重量％，更优选12-35重量％的载体；b) 5 to 60% by weight, preferably 10 to 45% by weight, more preferably 12 to 35% by weight of the carrier;
    其中各组分的总和加起来为100重量％。The sum of the components is added up to 100% by weight.
  2. 根据权利要求1的催化剂，其中沸石分子筛选自USY沸石分子筛、β沸石分子筛和丝光沸石分子筛中的一种或多种，优选为USY沸石分子筛和/或β沸石分子筛，更优选为USY沸石分子筛。The catalyst of claim 1 wherein the zeolite molecules are selected from one or more of the USY zeolite molecular sieves, beta zeolite molecular sieves, and mordenite molecular sieves, preferably USY zeolite molecular sieves and/or beta zeolite molecular sieves, more preferably USY zeolite molecular sieves.
  3. 根据权利要求1或2的催化剂，其中金属为Ni。A catalyst according to claim 1 or 2 wherein the metal is Ni.
  4. 根据权利要求1-3中任一项的催化剂，其中载体选自γ-Al 2O 3和二氧化硅中的一种或多种。 The catalyst according to any one of claims 1 to 3, wherein the carrier is selected from one or more of γ-Al 2 O 3 and silica.
  5. 一种制备根据权利要求1-4中任一项的催化剂的方法，所述方法包括如下步骤：A method of preparing a catalyst according to any one of claims 1 to 4, the method comprising the steps of:
    (1)提供SiO 2/Al 2O 3摩尔比为2-200，优选3-160，更优选5-120的H型沸石分子筛； (1) providing a H-type zeolite molecular sieve having a SiO 2 /Al 2 O 3 molar ratio of from 2 to 200 , preferably from 3 to 160, more preferably from 5 to 120;
    (2)将水溶性金属盐的水溶液与步骤(1)的H型沸石分子筛接触，然后过滤、清洗、干燥和焙烧，得到改性的沸石分子筛，其中所述金属选自Ni和Zn中的至少一种；和(2) contacting an aqueous solution of a water-soluble metal salt with the H-type zeolite molecular sieve of the step (1), followed by filtration, washing, drying and calcination to obtain a modified zeolite molecular sieve, wherein the metal is selected from at least Ni and Zn. One; and
    (3)将步骤(2)得到的改性的沸石分子筛与载体或载体前体、成型助剂、酸和水捏合，然后成型、干燥、焙烧、破碎和筛分，得到固体颗粒。(3) The modified zeolite molecular sieve obtained in the step (2) is kneaded with a carrier or a carrier precursor, a molding aid, an acid and water, and then shaped, dried, calcined, crushed and sieved to obtain solid particles.
  6. 根据权利要求5的方法，其中所述载体选自γ-Al 2O 3和二氧化硅中的至少一种；所述载体前体选自铝溶胶、拟薄水铝石、硅溶胶和粘土中的至少一种；所述成型助剂选自田箐粉、聚乙烯醇和聚乙二醇中的至少一种。 The method according to claim 5, wherein said carrier is at least one selected from the group consisting of γ-Al 2 O 3 and silica; and said carrier precursor is selected from the group consisting of aluminum sol, pseudoboehmite, silica sol and clay. At least one of; the forming aid is at least one selected from the group consisting of glutinous rice flour, polyvinyl alcohol, and polyethylene glycol.
  7. 一种使乙二醇单甲醚与异丁烯反应制备甲氧基乙基叔丁基醚的方法，所述方法在根据权利要求1-4中任一项的催化剂存在下进行。A process for preparing methoxyethyl tert-butyl ether by reacting ethylene glycol monomethyl ether with isobutylene, which is carried out in the presence of a catalyst according to any one of claims 1-4.
  8. 根据权利要求7的方法，其中乙二醇单甲醚与异丁烯的摩尔比为0.7-10:1，优选为0.8-5:1，更优选为0.9-2:1。A process according to claim 7 wherein the molar ratio of ethylene glycol monomethyl ether to isobutylene is from 0.7 to 10:1, preferably from 0.8 to 5:1, more preferably from 0.9 to 2:1.
  9. 根据权利要求7或8的方法，其中乙二醇单甲醚和异丁烯的质量空速为0.1-10h -1，优选为0.1-5h -1。 The process according to claim 7 or 8, wherein the mass space velocity of ethylene glycol monomethyl ether and isobutylene is from 0.1 to 10 h -1 , preferably from 0.1 to 5 h -1 .
  10. 根据权利要求7-9中任一项的方法，其中反应温度为30-100℃，优选50-70℃；反应压力为0.01-5.0MPa，优选0.1-3.0MPa。The process according to any one of claims 7 to 9, wherein the reaction temperature is from 30 to 100 ° C, preferably from 50 to 70 ° C; and the reaction pressure is from 0.01 to 5.0 MPa, preferably from 0.1 to 3.0 MPa.
  11. 根据权利要求1-4中任一项的催化剂在使乙二醇单甲醚与异丁烯反应制备甲氧基乙基叔丁基醚中的用途。Use of a catalyst according to any one of claims 1 to 4 for reacting ethylene glycol monomethyl ether with isobutylene to produce methoxyethyl tert-butyl ether.
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