阅读说明：本技术 一种叔丁醇精制催化剂及其制备方法和应用 (Tert-butyl alcohol refining catalyst and preparation method and application thereof ) 是由 徐会青 张信伟 李�杰 刘全杰 于 2019-10-28 设计创作，主要内容包括：本发明公开一种叔丁醇精制催化剂的制备方法,包括如下步骤：(1)配制含有铂络合物、介孔有机模板剂的混合液；(2)制备La改性的二氧化硅；(3)将步骤(1)配制的混合液同步骤(2)制备的La改性的二氧化硅混捏成型制得叔丁醇精制催化剂。所述方法制备的催化剂对叔丁醇原料中的有机过氧化物、有机酸酯等杂质具有优异的脱除能力,杂质脱除率达到99%以上。(The invention discloses a preparation method of a tertiary butanol refining catalyst, which comprises the following steps: (1) preparing a mixed solution containing a platinum complex and a mesoporous organic template; (2) preparing La modified silicon dioxide; (3) and (3) kneading the mixed solution prepared in the step (1) and the La modified silicon dioxide prepared in the step (2) to form the tert-butyl alcohol refining catalyst. The catalyst prepared by the method has excellent removal capacity for impurities such as organic peroxide, organic acid ester and the like in the tert-butyl alcohol raw material, and the removal rate of the impurities reaches more than 99%.)

1. A preparation method of a tertiary butanol refining catalyst comprises the following steps:

(1) preparing a mixed solution containing a platinum complex and a mesoporous organic template;

(2) preparing La modified silicon dioxide;

(3) and (3) kneading the mixed solution prepared in the step (1) and the La modified silicon dioxide prepared in the step (2) to form the tert-butyl alcohol refining catalyst.

2. The method of claim 1, wherein: the platinum complex in the step (1) is one or more of dichloro-1, 2-cyclohexanediamine platinum, 1-cyclobutane dicarboxylic acid diammine platinum and 1, 2-diaminocyclohexane oxalic acid platinum.

3. The method of claim 1, wherein: the mesoporous organic template agent in the step (1) is one or more of polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, polyoxyethylene polyoxypropylene ether block copolymer and fatty alcohol-polyoxyethylene ether.

4. The method of claim 1, wherein: the method is characterized in that: the mass content of the platinum complex in the mixed solution in the step (1) is 0.5-10% calculated by Pt elementary substance; the mass content of the mesoporous organic template agent is 0.5-10%.

5. The method of claim 1, wherein: and (2) adjusting the pH value of the mixed solution to 2-5 in the step (1).

6. The method of claim 1, wherein: the mixed solution in the step (1) contains macromolecular organic matters, and the macromolecular organic matters are selected from one or more of synthetic cellulose, polymeric alcohol, acrylic acid polymer with the molecular weight of 200-10000 and maleic acid copolymer.

7. The method of claim 6, wherein: the synthetic cellulose is selected from one or more of carboxymethyl cellulose, methyl cellulose, ethyl cellulose and hydroxy cellulose; the polymeric alcohol is selected from one or more of polyethylene glycol, polypropylene alcohol and polyvinyl alcohol.

8. The method according to claim 6 or 7, characterized in that: the mass content of the macromolecular organic matters in the mixed solution is 0.5-10%.

9. The method of claim 1, wherein: in the step (2), the La modified silicon dioxide is prepared by loading La on silicon dioxide powder, the mass content of lanthanum in the La modified silicon dioxide is 0.5-10% in terms of oxide, and the lanthanum precursor is one or more of corresponding nitrate, sulfate and chloride.

10. The method of claim 9, wherein: loading La on the silicon dioxide powder by an impregnation method, drying and roasting to obtain the catalyst.

11. The method of claim 10, wherein: the drying temperature is 80-220 ℃; the drying time is 6 to 48 hours.

12. The method of claim 1, wherein: and (3) adding one or more of peptizing agent and extrusion aid in the forming process, wherein the drying and roasting conditions after forming are as follows: the drying temperature is 80-200 ℃, and the drying time is 6-48 hours; the roasting is carried out in an oxygen-containing atmosphere, and the roasting condition is that the roasting temperature is 300-800 ℃, and the roasting time is 4-10 hours.

13. A catalyst prepared by the process of any one of claims 1 to 12, wherein: based on the weight of the final catalyst, the content of Pt in terms of simple substance is 0.1% -1.0%; the content of lanthanum is 0.5-10.0% calculated by oxide.

14. The catalyst of claim 13 for use in the purification of t-butanol, characterized by: the reaction conditions were as follows: adopting a fixed bed reactor, wherein the tert-butyl alcohol raw material: the mass ratio of water is (20-120): 1; the volume ratio of the tert-butyl alcohol raw material to the hydrogen is (10-100): 1; the volume space velocity of the tert-butyl alcohol raw material is 0.5 h^-1～3.0 h^-1(ii) a The reaction temperature is 150-300 ℃; the reaction pressure is 0.5 MPa-5 MPa.

Technical Field

The invention relates to a tert-butyl alcohol (TBA) refined catalyst, a preparation method and application thereof, in particular to a high-activity tert-butyl alcohol (TBA) refined catalyst, and a preparation method and application thereof.

Background

Propylene oxide is the third largest propylene derivative besides polypropylene and acrylonitrile, and is an important basic organic chemical raw material. The method is mainly used for producing polyether polyol, nonionic surfactant, propylene carbonate and propylene glycol, is an important raw material of fine chemical products, and is widely applied to industries such as automobiles, buildings, food, tobacco, medicine, cosmetics and the like.

The existing propylene oxide production technology mainly comprises the following steps: chlorohydrin process, co-oxidation process, direct oxidation process. The environmental disadvantages of the chlorohydrin process have led to the gradual market withdrawal of this route. The new project mainly considers the co-oxidation method and the direct oxidation method. The co-oxidation process comprises: ethylbenzene co-oxidation (PO/SM), isobutane co-oxidation (PO/TBA, PO/MTBE), cumene oxidation (CHP). The PO/MTBE combination comprises: the method comprises the unit processes of iso-butane oxidation, propylene epoxidation, product separation and purification, TBA refining, MTBE synthesis and the like. Among them, the TBA material after epoxidation contains impurities such as organic acid esters, peroxides, etc., which may adversely affect the subsequent synthesis of MTBE. Therefore, before entering the MTBE synthesis unit, the TBA is purified to remove impurities.

The TBA feedstock from the PO/MTBE complex contains a variety of impurities, including organic acid ester impurities: tert-butyl formate (TBF), isobutyl formate (IBF), organic peroxide impurities including: t-butyl hydroperoxide (TBHP), di-t-butyl peroxide (DTBP). These four impurities have negative effects on downstream processes and therefore must be treated to remove the impurities before entering the downstream processes.

Disclosure of Invention

Aiming at the defects of the prior art, the invention provides a tertiary butanol refining catalyst, a preparation method and application thereof. The catalyst has excellent removal capability on impurities such as organic peroxides (TBHP, DTBP), organic acid esters (TBF, IBF) and the like in TBA raw materials, and the removal rate of the impurities reaches more than 99%.

A preparation method of a tertiary butanol refining catalyst comprises the following steps:

(1) preparing a mixed solution containing a platinum complex and a mesoporous organic template;

(2) preparing La modified silicon dioxide;

(3) and (3) kneading the mixed solution prepared in the step (1) and the La modified silicon dioxide prepared in the step (2) to form the tert-butyl alcohol refining catalyst.

In the above method, the platinum complex is an organic platinum complex, wherein the organic platinum complex is preferably one or more of dichloro-1, 2-cyclohexanediamine platinum, 1-cyclobutane dicarboxylic acid diammine platinum and 1, 2-diaminocyclohexane oxalic acid platinum, and more preferably 1, 1-cyclobutane dicarboxylic acid diammine platinum.

In the above method, the mesoporous organic template is preferably one or more of an ethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123), a polyoxyethylene polyoxypropylene ether block copolymer (F127), and fatty alcohol polyoxyethylene ether (AEO), and more preferably an ethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123).

In the above method, the mass content (in terms of Pt) of the platinum complex in the mixed solution is 0.5% to 10%, preferably 1.0% to 5%; the mass content of the mesoporous organic template agent is 0.5-10%, preferably 1.0-5.0%, and the balance is water.

In the above method, the pH of the mixed solution is adjusted to 2 to 5, preferably 2 to 3, and the acidic solution used is acetic acid or hydrochloric acid, preferably acetic acid. The pH value of the mixed solution is adjusted to ensure that the platinum complex is further and intensively adsorbed on the mesoporous organic template.

In the method, the mixed solution further contains macromolecular organic matter, and the macromolecular organic matter is selected from one or more of synthetic cellulose, polymeric alcohol, acrylic acid polymer with molecular weight of 200-10000 and maleic acid copolymer. The synthetic cellulose is selected from one or more of carboxymethyl cellulose, methyl cellulose, ethyl cellulose and hydroxy cellulose. The polymeric alcohol is selected from one or more of polyethylene glycol, polypropylene alcohol and polyvinyl alcohol. The mass content of the macromolecular organic matter in the mixed solution is 0.5-10%, preferably 1.0-5.0%.

In the above method, the La-modified silica is obtained by supporting La on a silica powder, for example, by introducing La to a silica powder by an impregnation method and drying. The drying temperature is 80-220 ℃, and preferably 120-180 ℃; the drying time is 6-48 hours, and the drying time is 10-20 hours. The La-modified silicon dioxide contains 0.5-10% of lanthanum calculated by oxide, and preferably 1.0-5.0%. The lanthanum precursor is one or more of nitrate, sulfate and chloride of the lanthanum precursor, and preferably nitrate.

In the method, one or more of a peptizing agent and an extrusion assistant can be added in the step (3) during the forming process. The drying and roasting conditions after molding are as follows: the drying temperature is 80-200 ℃, and the drying time is 6-48 hours; the roasting is carried out in an oxygen-containing atmosphere, and the roasting condition is that the roasting temperature is 300-800 ℃, and the roasting time is 4-10 hours.

The tertiary butanol refining catalyst prepared by the method comprises the following components, by weight, 0.1% -1.0% of Pt in terms of simple substance, preferably 0.2% -0.5%; the lanthanum content, calculated as oxide, is between 0.5% and 10.0%, preferably between 1.0% and 5.0%.

The catalyst is used for refining tertiary butanol, and the catalyst needs to be pretreated before use, namely, the hydrogenation active metal component is converted into an elemental substance, and wet reduction or dry reduction can be adopted, and dry reduction is preferred. The dry reduction can adopt pure hydrogen or hydrogen containing inert gas, wherein the volume content of the hydrogen is 5-100%, and preferably 50-100%; the reduction conditions were as follows: the pressure is normal pressure to 10MPa, preferably 2 MPa to 8 MPa; the temperature is 200-600 ℃, preferably 300-400 ℃; the reduction time is 2 to 12 hours, preferably 2 to 6 hours, and the volume ratio of the gas agent (i.e. the volume ratio of the hydrogen to the catalyst) is 500 to 1500, preferably 800 to 1200.

The catalyst is used for refining tertiary butanol, and the reaction conditions are as follows: adopting a fixed bed reactor, wherein the tert-butyl alcohol raw material: the mass ratio of water is (20-120): 1, preferably (80-100): 1; the volume ratio of the tert-butyl alcohol raw material to the hydrogen is (10-100): 1, preferably (20-40): 1; the space velocity of the feeding volume is 0.5 h^-1～3.0 h^-1Preferably 1.5 h^-1～2.5 h^-1(ii) a The reaction temperature is 150-30 DEG C0 ℃, preferably 170 ℃ to 210 ℃; the reaction pressure is 0.5MPa to 5MPa, preferably 1.5MPa to 3 MPa.

Compared with the prior art, the method can effectively remove impurities in the tert-butyl alcohol raw material to obtain the refined tert-butyl alcohol.

Detailed Description

The action and effect of the present invention will be further described below with reference to examples and comparative examples, but the following examples and comparative examples are not intended to limit the present invention, and the% in the present invention is not particularly limited as long as it is a mass percentage.

The chromatographic analysis conditions of the tert-butyl alcohol raw material and the product are as follows: an Agilent 7890A gas chromatograph, a FID detector and a DB-1301 chromatographic column, and an internal standard method is adopted for quantitative analysis, wherein the internal standard substance is benzyl alcohol. The calculation method of the impurity removal rate comprises the following steps:

example 1

Adding 10 g of 1, 1-cyclobutane dicarboxylic acid diammine platinum and 5.0 g of P123 into 100g of deionized water, adding acetic acid to adjust the pH value to be about 2, stirring at normal temperature for 20min to form a platinum-containing organic template agent, adding 5.0 g of carboxymethyl cellulose (with the molecular weight of 3000) into the solution, and continuously stirring at normal temperature for 40min to obtain a platinum-containing precursor required by the experiment, wherein the sample number is Sov-1.

Weighing 50g of silicon dioxide (with particle size of 80 nm), adding 150ml of distilled water, stirring to mix uniformly, and weighing lanthanum nitrate (La) to obtain₂O₃Calculated) is added into the solution according to the mass percentage (based on the weight of the catalyst) of 2.5 percent, and the reaction is stopped after the stirring is carried out for 42 hours at normal temperature; drying at 150 ℃ for 5 hours, and roasting at 650 ℃ for 5 hours to obtain the catalytic material precursor, numbered AS-1, required by the experiment.

Sov-1 was mixed with AS-1, and 25% (based on the weight of the catalyst, the same applies hereinafter) of ammonia type silica Sol (SiO) was added₂30 percent of starch and 10 percent of water in percentage by mass in successionThe materials were thoroughly mixed under stirring and kneaded to give a plastic paste, which was shaped into a cylindrical orifice plate having a diameter of 2.0mm, then dried at 120 ℃ for 12 hours and calcined at 550 ℃ for 4 hours to obtain the catalyst of the present invention, No. A1.

The catalyst evaluation is carried out in a fixed bed continuous micro flow reactor, the catalyst is reduced for 4 hours at 350 ℃ in the hydrogen atmosphere in advance, after the reduction is finished, the temperature of the reactor is reduced to a set value, and the raw material is introduced for carrying out the tertiary butanol refining reaction. The reaction conditions are as follows: the volume ratio of the tert-butyl alcohol raw material to the hydrogen is 30: 1; the space velocity of the feeding volume is 2.5 h^-1(ii) a The reaction temperature is 190 ℃; the reaction pressure was 2.0 MPa.

The catalyst composition is shown in Table 1, and the reaction results are shown in Table 2.

Example 2

Catalyst preparation and evaluation the same as example 1 except that: in the step 1, the carboxymethyl cellulose is changed into polyvinyl alcohol (molecular weight is 2000) powder, the content is 1.8 percent, and the numbering is as follows: sov-2.

The catalyst composition is shown in Table 1, and the reaction results are shown in Table 2.

Example 3

Catalyst preparation and evaluation the same as example 1 except that: 1, 2-diaminocyclohexane platinum oxalate is used for replacing 1, 1-diaminobutane dicarboxylic acid diammine platinum, carboxymethyl cellulose is changed into polypropylene alcohol (molecular weight is 2000) powder, and the mixture is stirred for 50min at normal temperature, and is numbered Sov-3.

The catalyst composition is shown in Table 1, and the reaction results are shown in Table 2.

Example 4

Catalyst preparation and evaluation the same as example 1 except that: 1, 2-diaminocyclohexane platinum oxalate is used to replace 1, 1-diaminobutane dicarboxylic acid diammine platinum, and carboxymethyl cellulose is changed into acrylic acid polymer (molecular weight: 1500), number Sov-4.

The catalyst composition is shown in Table 1, and the reaction results are shown in Table 2.

Example 5

Catalyst preparation and evaluation the same as example 1 except that: dichloro-1, 2-cyclohexanediamine platinum is used for replacing 1, 1-cyclobutane dicarboxylic acid diammine platinum, and carboxymethyl cellulose (molecular weight is 3000) is changed into carboxymethyl cellulose (molecular weight is 4000) with the number of Sov-5.

The catalyst composition is shown in Table 1, and the reaction results are shown in Table 2.

Example 6

Catalyst preparation and evaluation the same as example 1 except that: platinum diammine 1, 1-cyclobutanedicarboxylate was added to F127, numbered: sov-6. The drying temperature was 120 ℃ and the drying time was 16 hours.

The catalyst composition is shown in Table 1, and the reaction results are shown in Table 2.

Example 7

Catalyst preparation and evaluation the same as example 1 except that: 1, 1-cyclobutane dicarboxylic acid diammine platinum is added into AEO, carboxymethyl cellulose is changed into polyethylene glycol (molecular weight is 3000), and the code is as follows: sov-7. The drying temperature is 170 ℃, and the drying time is 24 hours; the calcination temperature of the carrier was 550 ℃ and the calcination time was 7.5 hours.

The catalyst composition is shown in Table 1, and the reaction results are shown in Table 2.