CN110252394B - Catalyst for preparing propylene oxide by propylene oxidation, preparation and application thereof - Google Patents
Catalyst for preparing propylene oxide by propylene oxidation, preparation and application thereof Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
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- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
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- C—CHEMISTRY; METALLURGY
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- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
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- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
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- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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Abstract
The invention belongs to the technical field of catalyst preparation, and particularly relates to a catalyst for preparing propylene oxide by propylene oxidation, and preparation and application thereof. The modified titanium silicon molecular sieve membrane catalyst takes alumina as a carrier, and a titanium silicon molecular sieve membrane is loaded on the surface of the carrier, wherein P is also loaded on the surface of the titanium silicon molecular sieve membrane2O5. The modified titanium silicon molecular sieve membrane catalyst has the characteristics of large effective specific surface area, high catalyst activity and good catalyst stability, and can be used for preparing a catalyst for the treatment of high-temperature oxidation of hydrocarbons in the presence of hydrogen2O2More effective active phase TiOO-H (HPO) can be generated in the system4) Finally, the activity and stability of the catalyst are obviously improved compared with the existing titanium silicalite molecular sieve catalyst and titanium silicalite membrane catalyst.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a catalyst for preparing propylene oxide by propylene oxidation, and preparation and application thereof.
Background
Propylene oxide, namely methyl ethylene oxide or Propylene Oxide (PO), is one of three important basic organic chemical synthesis raw materials, has the yield and the consumption second to polypropylene, is a second derivative of propylene, is mainly used for producing polyether polyol and further processing into polyurethane, and the application field of the polyurethane relates to various aspects of basic industry, national defense and daily life of people. The method can also be used for producing chemical substances such as propylene glycol, propylene glycol ether, nonionic surfactant, flame retardant and the like, and has wide application in industries such as automobiles, buildings, food, tobacco, medicine, cosmetics and the like. Therefore, the research and development of the high-efficiency, economical and environment-friendly propylene oxide production process and catalyst have important significance.
Currently, industrial PO production methods in the world mainly include a chlorohydrin method, a co-oxidation method, an oxygen direct oxidation method and a hydrogen peroxide direct oxidation method (HPPO method). Among them, the chlorohydrin method has been gradually replaced by new processes due to its characteristics of consuming a large amount of chlorine in the production process, causing severe corrosion to equipment, and having a large influence on the environment by chlorine-containing wastewater. The co-oxidation method is characterized by long industrial process, large investment, various product types, and direct influence on the overall PO benefit due to the price and market demand of byproducts. The direct oxygen oxidation method has been widely studied as an emerging means for preparing propylene oxide, but the method has few industrial applications and is still in the basic research stage.
The HPPO method is derived from the production process of epoxidation reaction by Enichem company of Italy with TS-1 as catalyst and hydrogen peroxide as oxidant. The method prepares the propylene oxide by direct oxidation reaction in a fixed bed reactor, has mild reaction conditions, and is favorable for coming out since the market. The process overcomes the defects of serious corrosion of chlorohydrination method equipment and more waste liquid and waste residue, has simple industrial process, high product yield, only generates epoxypropane and water in the production process, does not produce co-produced products, has less discharge of three wastes, can recycle raw materials and auxiliary agents, has low infrastructure cost, low energy consumption and less pollution, is mature in industrialization, has been applied in a large scale, and shows good prospect.
US4410501 discloses for the first time a synthesis process for TS-1 molecular sieves, and patents represented by US7378536, US7449590 disclose a process for the preparation of propylene oxide using hydrogen peroxide in the presence of a titanium silicalite molecular sieve catalyst and in the presence of a methanol solvent. However, the titanium silicalite molecular sieve is used as a catalyst, and is influenced by the specific area and the pore size of the TS-1 molecular sieve, so that the conversion rate of propylene and the selectivity of PO are relatively low, and the stability of the catalyst is relatively poor.
The prior art also discloses further improvements to such catalysts. For example, US3923843 and US4367342 disclose amorphous silica supported titanium supported catalysts for the preparation of propylene oxide. However, since the specific surface area and pore volume of amorphous silica are too small, the content of Ti is difficult to increase, affecting the activity and stability of the catalyst. US4701428 reports a spray drying process for preparing titanium silicalite molecular sieves, however, the catalyst particles of this process are only 20 microns, which is difficult to use in fixed bed reactors.
CN1268400A discloses a method for preparing a titanium silicalite molecular sieve as an active component of a catalyst by mixing, extruding or tabletting with alumina, so that the particles of the catalyst can be set according to the requirements of an industrial fixed bed reactor. Meanwhile, acetate is adopted for treatment, the overall activity of the catalyst is improved, the catalyst reacts with hydrogen peroxide under the conditions that the reaction temperature is 40 ℃ and the reaction pressure is 0.4MPa, the conversion rate of H2O2 reaches 93.4 percent, and the selectivity of propylene oxide reaches 95.7 percent.
CN102822158A discloses a method for preparing a catalyst by pretreating a TS-1 molecular sieve with a methanol solution, wherein methanol is not additionally added in industrial use, and the activity of the catalyst is equivalent to that of a methanol solvent. Therefore, the activity and stability of the catalyst are relatively weak.
US8785670B2 and WO2012076543a1 describe techniques for effectively increasing the conversion of H2O2 and the selectivity of PO by adding specific potassium salts of phosphorus-containing oxyacids to the feed stream. The total conversion rate of H2O2 by adopting the process is more than or equal to 99.8 percent, and the purity of PO reaches more than or equal to 99.99 percent. But the overall stability of the catalyst is relatively weak due to the specific surface area and pore volume of the catalyst.
Meanwhile, in the past 15 years, a great deal of literature is available for research reports on titanium silicon molecular sieve membranes, such as CN100999324A and CN 101003012A. Compared with a titanium silicalite molecular sieve, the titanium silicalite molecular sieve membrane has high heat resistance, high mechanical strength and high chemical stability, and has important research significance in the fields of membrane catalysis and membrane separation. The titanium-silicon molecular sieve can be grown on the porous material by crystallization to synthesize a titanium-silicon molecular sieve membrane which is used as an efficient catalyst for efficiently catalyzing a series of H2O2Participating in organic oxidation reaction.
However, no research and application of the titanium silicalite membrane in the reaction of preparing propylene oxide by propylene oxidation is available at present; moreover, in specific practice, it has been found that the activity and stability are not very desirable when the existing titanium silicalite membrane is directly used as a catalyst for preparing propylene oxide by propylene oxidation.
Disclosure of Invention
In order to overcome the technical problems, the invention provides a modified titanium silicalite membrane catalyst. The modified titanium silicon molecular sieve membrane catalyst has the characteristics of large effective specific surface area, high catalyst activity and good catalyst stability.
The modified titanium silicon molecular sieve membrane catalyst takes alumina as a carrier, and a titanium silicon molecular sieve membrane is loaded on the surface of the carrier, wherein P is further loaded on the surface of the titanium silicon molecular sieve membrane2O5。
The invention takes the titanium silicon molecular sieve membrane/alumina carrier as the basal body to carry out the phosphorus modification,the titanium-silicon molecular sieve membrane can be fully dispersed on the surface of the alumina carrier, and the defects of small specific surface area and small pore volume of the existing titanium-silicon molecular sieve are overcome; the obtained catalyst has larger pore volume, so that the effective specific surface area and the number of catalytic active sites can be obviously improved. Meanwhile, the invention can improve the effective activity of the catalyst Ti by modifying the phosphorus of the titanium-silicon molecular sieve membrane, thereby further improving the activity of the catalyst Ti in H2O2More effective active phase TiOO-H (HPO) is generated in the system4) Finally, the activity and stability of the catalyst are obviously improved compared with the existing titanium silicalite molecular sieve catalyst and titanium silicalite membrane catalyst.
In the modified titanium silicon molecular sieve membrane catalyst, the P2O5The mass fraction of (A) is 0.1-3 wt%, preferably 1-2.5 wt%, and in the range, the best active intermediate can be generated in a matching way, so that the activity and stability of the catalyst are improved.
In the modified titanium-silicon molecular sieve membrane catalyst, the titanium-silicon molecular sieve membrane accounts for 10-40 wt%, preferably 20-30 wt%. The catalyst obtained in the range has better catalytic activity and stability.
The alumina is selected from gamma-Al2O3Preferably, the specific surface area is 180 to 250m2gamma-Al with a pore volume of 0.41-0.80 ml/g2O3. It has the characteristics of larger specific surface area and large pore volume, and is more beneficial to the loading and P of the titanium-silicon molecular sieve2O5The effect of highly dispersing active sites is achieved.
The invention also provides a preparation method of the catalyst, which comprises the following steps: modifying the alumina carrier loaded with the titanium-silicon molecular sieve membrane by using a phosphorus-containing modifier by adopting an isometric impregnation method, drying and roasting to obtain the titanium-silicon molecular sieve membrane.
The phosphorus-containing modifier is selected from one or more of phosphoric acid, diammonium hydrogen phosphate, ammonium dihydrogen phosphate or potassium dihydrogen phosphate, and potassium dihydrogen phosphate is preferred; researches show that the stability of the catalyst can be further improved by adopting potassium dihydrogen phosphate for modification.
The drying temperature is 100-140 ℃, preferably 120-130 ℃; researches show that under the condition, the phosphorus-containing compound can be more uniformly dispersed on the surface of the catalyst, so that the specific surface area of the catalyst is further improved, and the activity and the stability of the catalyst are improved.
The roasting temperature is 400-600 ℃, preferably 550-560 ℃; experiments show that the acidic function of the obtained catalyst is optimal under the conditions.
In a preferred embodiment of the invention, the titanium-silicon molecular sieve membrane-loaded alumina carrier is obtained by performing impregnation modification, drying at 120 ℃ for 24 hours, and roasting at 550 ℃ for 4 hours.
The alumina carrier loaded with the titanium-silicon molecular sieve membrane can be prepared by adopting a conventional method in the field, such as mixing a silicon source, a titanium source, a template agent and water, adding the alumina carrier, crystallizing, filtering, drying and roasting to obtain the titanium-silicon molecular sieve membrane.
As a preferred embodiment, the alumina carrier for supporting the titanium silicalite membrane can be prepared by adopting the following method: tetrapropylammonium hydroxide (TPAOH) is used as a template agent, tetraethyl orthosilicate is used as a silicon source, tetrabutyl titanate is used as a titanium source, the crystallization is carried out, the filtration and washing are carried out to neutrality, the drying is carried out for 12h in a drying box at the temperature of 80 ℃, and finally the roasting is carried out for 6 h in a muffle furnace at the temperature of 550 ℃, thus obtaining the catalyst.
The invention also provides application of the modified titanium-silicon molecular sieve membrane catalyst in an HPPO (high pressure propylene oxide) method, preferably in an H-type catalyst2O2In the reaction of preparing propylene oxide from propylene as oxidant, more active TiOO-H (HPO4) phase can be generated to increase the activity of catalyst.
The invention also provides propylene in H2O2A method for producing propylene oxide by oxidation reaction in a system, comprising: after the modified titanium-silicon molecular sieve membrane catalyst is loaded into a fixed bed reactor, mixing propylene, methanol and hydrogen peroxide, and then feeding the mixture into the reactor, wherein the propylene and the hydrogen peroxide are subjected to an epoxidation reaction on a catalyst bed layer to generate a mixed solution containing propylene, propylene oxide, methanol and water; wherein the reaction temperature is 80-160 ℃; the pressure is 1.5-3.5 MPa, and the feeding airspeed is 3.0-6.0h-1(ii) a The mol ratio of the propylene to the hydrogen peroxide is 1.0-3.0. Experiments show that the invention is adoptedCan obviously increase H2O2Conversion of (a), selectivity of PO and yield of PO.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
Example 1
This example provides a preparation method of a modified titanium silicalite membrane catalyst, which includes:
(1) preparing tetrapropylammonium hydroxide (TPAOH) solution as a template agent, and preparing SiO according to a molar ratio2:TiO2:TPAOH:H2The titanium silicalite membrane was prepared with O ═ 1.0:0.03:0.18: 18:
TPAOH (20 wt%) was first mixed with water to form a solution A containing 10.62% by weight of TPAOH, also as SiO2:TiO2Tetraethyl orthosilicate (silicon source) and tetrabutyl titanate (titanium source) were selected for mixing in a ratio of 1.0:0.03 to form solution B. Slowly adding the solution B into the solution A, stirring for 30min, putting the uniformly mixed solution at 50 ℃ for hydrolysis, and removing alcohol until the solution is clear; then a certain amount of alumina (titanium silicalite 10% of the total catalyst) was added to the solution and crystallized in a homogeneous reaction vessel containing a polytetrafluoroethylene liner for 2 days.
And (3) carrying out suction filtration and washing on the obtained titanium-silicon molecular sieve membrane/alumina carrier until the titanium-silicon molecular sieve membrane/alumina carrier is neutral, then placing the titanium-silicon molecular sieve membrane/alumina carrier in a drying oven at 80 ℃ for drying for 12h, and finally roasting the titanium-silicon molecular sieve membrane/alumina carrier in a muffle furnace at 550 ℃ for 6 h to finally obtain the titanium-silicon molecular sieve membrane/alumina carrier A containing 10% of titanium-silicon molecular sieves in mass fraction.
(2) Weighing two parts of carrier A with equal mass, and impregnating potassium dihydrogen phosphate aqueous solutions with different concentrations by adopting an isovolumetric impregnation method to obtain load P2O5The catalyst with equivalent percentage content of 1% and 2% respectively is naturally aired, dried at 120 ℃ for 24h and roasted at 550 ℃ for 4h, and finally the prepared catalyst is A1/A2 in number.
Example 2
This example provides a preparation method of a modified titanium silicalite membrane catalyst, which includes:
(1) according to the preparation method of the embodiment 1, the titanium-silicon molecular sieve membrane/alumina carrier B containing 20% of titanium-silicon molecular sieve by mass is prepared by adjusting the mass ratio of the titanium-silicon molecular sieve membrane to the alumina carrier.
(2) Weighing two parts of carrier B with equal mass, and impregnating potassium dihydrogen phosphate aqueous solutions with different concentrations by adopting an isovolumetric impregnation method to obtain P2O5The equivalent weight percentage of the catalyst is respectively 1% and 2%, then the catalyst is naturally aired, dried at 120 ℃ for 24 hours and roasted at 550 ℃ for 4 hours, and finally the prepared catalyst is respectively B1/B2 in number.
Example 3
This example provides a preparation method of a modified titanium silicalite membrane catalyst, which includes:
(1) according to the preparation method of the embodiment 1, the titanium-silicon molecular sieve membrane/alumina carrier C containing the titanium-silicon molecular sieve with the mass fraction of 30% is prepared by adjusting the mass ratio of the titanium-silicon molecular sieve membrane to the alumina carrier.
(2) Weighing two parts of carrier C with equal mass, and impregnating potassium dihydrogen phosphate aqueous solutions with different concentrations by adopting an isovolumetric impregnation method to obtain P2O5The catalyst with equivalent percentage content of 1% and 2% respectively is naturally aired, dried at 120 ℃ for 24h and roasted at 550 ℃ for 4h, and finally the prepared catalyst is respectively C1/C2 in number.
Example 4
This example provides a preparation method of a modified titanium silicalite membrane catalyst, which includes:
(1) according to the preparation method of the embodiment 1, the titanium-silicon molecular sieve membrane/alumina carrier D containing 40% of titanium-silicon molecular sieve by mass is prepared by adjusting the mass ratio of the titanium-silicon molecular sieve membrane to the alumina carrier.
(2) Weighing two parts of carrier D with equal mass, and impregnating potassium dihydrogen phosphate aqueous solutions with different concentrations by adopting an isovolumetric impregnation method to obtain P2O5The catalyst with equivalent percentage content of 1% and 2% respectively is naturally aired, dried at 120 ℃ for 24h and roasted at 550 ℃ for 4h, and finally the prepared catalyst is respectively D1/D2 in number.
Comparative example 1
The supports A/B/C/D obtained in examples 1 to 4 were used as comparative catalysts, i.e., titanium silicalite membrane catalysts which were not modified with a phosphorus-containing solution, respectively.
Comparative example 2
The titanium silicalite prepared according to the method of example 1 was used as a comparative catalyst E, i.e., the titanium silicalite obtained in example 1 without using an alumina support.
Evaluation of catalyst
The method comprises the following steps:
the method comprises the steps of respectively filling the above 8 n-alkane low-temperature isomerization catalysts (Cat A1, Cat A2, Cat B1, Cat B2, Cat C1, Cat C2, Cat D1, Cat D2 and comparative catalysts (Cat A, Cat B, Cat C, Cat D and Cat E) into a fixed bed reactor, mixing propylene, methanol and hydrogen peroxide from the reactor, then feeding the mixture into the reactor, and carrying out epoxidation reaction on the propylene and the hydrogen peroxide on a catalyst bed layer to generate a mixed solution containing the propylene, the propylene oxide, the methanol and water.
The reaction temperature of the catalyst bed layer is 140 ℃, the pressure is 2.1MPa, and the space velocity of the feeding is 3.0-6.0h-1The mol ratio of propylene to hydrogen peroxide is 2.0.
Measuring the content of hydrogen peroxide by potentiometric titration, and measuring the content of other organic substances by chromatography.
The calculation formula is as follows:
data processing:
hydrogen peroxide conversion rate-H consumed2O2amount/H2O2Initial amount
Selectivity to propylene oxide-H consumed by PO formation2O2Amount of (A)/H2O2Amount of consumption
Yield of propylene oxide (hydrogen peroxide conversion) and selectivity of propylene oxide
The final catalyst evaluation results are shown in table 1.
Table 1 evaluation results of catalyst performance:
| catalyst numbering | H2O2Conversion in wt.% | PO selectivity, wt% | PO yield% |
| Cat A1 | 93.1 | 88.7 | 82.6 |
| Cat A2 | 94.2 | 90.1 | 84.9 |
| Cat B1 | 96.4 | 94.1 | 90.7 |
| Cat B2 | 97.1 | 95.2 | 92.4 |
| Cat C1 | 96.8 | 94.5 | 91.5 |
| Cat C2 | 97.5 | 96.5 | 94.1 |
| Cat D1 | 92.5 | 89.6 | 82.9 |
| Cat D2 | 93.3 | 90.1 | 84.1 |
| Comparative Cat A | 85.1 | 83.5 | 71.1 |
| Comparative Cat B | 84.6 | 84.1 | 71.1 |
| Comparative Cat C | 86.6 | 85.3 | 73.9 |
| Comparative Cat D | 85.6 | 83.2 | 71.2 |
| Comparative Cat E | 84.5 | 82.3 | 69.5 |
As can be seen by comparing the reaction data in Table 1, the catalysts obtained in examples 1-4 have higher H than the comparative catalyst2O2Conversion, PO selectivity and PO yield, with catalysts B2 and C2 performing best.
Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (13)
1. A modified titanium silicon molecular sieve membrane catalyst takes alumina as a carrier, and a titanium silicon molecular sieve membrane is loaded on the surface of the carrier, and is characterized in that a roasted product containing a phosphorus modifier is loaded on the surface of the titanium silicon molecular sieve membrane;
the phosphorus-containing modifier is selected from one or more of phosphoric acid, diammonium hydrogen phosphate, ammonium dihydrogen phosphate or potassium dihydrogen phosphate;
with P2O5The mass fraction of the P element in the roasted product is 1-2.5 wt%;
the titanium silicon molecular sieve membrane accounts for 20-30 wt% of the mass fraction;
the loading method comprises the following steps: modifying the alumina carrier loaded with the titanium-silicon molecular sieve membrane by using a phosphorus-containing modifier by adopting an isometric impregnation method, drying and roasting; the roasting temperature is 400-600 ℃.
2. The modified titanium silicalite membrane catalyst of claim 1, wherein the alumina is selected from the group consisting of γ -Al2O3。
3. The modified titanium silicalite membrane catalyst of claim 2, wherein the alumina is selected from the group consisting of alumina having a specific surface area of 180 to 250m2gamma-Al with a pore volume of 0.41-0.80 ml/g2O3。
4. The method for preparing the modified titanium silicalite membrane catalyst of any one of claims 1 to 3, comprising: modifying the alumina carrier loaded with the titanium-silicon molecular sieve membrane by using a phosphorus-containing modifier by adopting an isometric impregnation method, drying and roasting to obtain the titanium-silicon molecular sieve membrane.
5. The preparation method of claim 4, wherein the phosphorus-containing modifier is selected from one or more of phosphoric acid, diammonium hydrogen phosphate, ammonium dihydrogen phosphate or potassium dihydrogen phosphate.
6. The method of claim 5, wherein the phosphorus-containing modifier is potassium dihydrogen phosphate.
7. The method according to any one of claims 4-6, wherein the drying temperature is 100-140 ℃.
8. The method as claimed in claim 7, wherein the drying temperature is 120-130 ℃.
9. The method according to any one of claims 4-6, wherein the temperature of the calcination is 400-600 ℃.
10. The method as claimed in claim 9, wherein the temperature of the calcination is 550-560 ℃.
11. The process according to any one of claims 4 to 6, wherein tetrapropylammonium hydroxide is used as a template, tetraethyl orthosilicate is used as a silicon source, and tetrabutyl titanate is used as a titanium source.
12. The modified titanium-silicon molecular sieve membrane catalyst of any one of claims 1 to 3, which is prepared by using H in HPPO method2O2In the preparation of propylene oxide from propylene as oxidantApplication is carried out.
13. Propylene in H2O2The method for generating the propylene oxide through the oxidation reaction in the system is characterized by comprising the following steps:
after the modified titanium silicon molecular sieve membrane catalyst of any one of claims 1 to 3 is loaded into a fixed bed reactor, propylene, methanol and hydrogen peroxide are mixed and then enter the reactor, and the propylene and the hydrogen peroxide are subjected to epoxidation reaction on a catalyst bed layer to generate a mixed solution containing the propylene, the propylene oxide, the methanol and water;
wherein the reaction temperature is 80-160 ℃; the pressure is 1.5-3.5 MPa, and the feeding airspeed is 3.0-6.0h-1(ii) a The mol ratio of the propylene to the hydrogen peroxide is 1.0-3.0.
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| CN114345405B (en) * | 2021-12-28 | 2023-09-19 | 万华化学集团股份有限公司 | Load-formed titanium-silicon molecular sieve and preparation method thereof, and preparation method of benzenediol |
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| CN108654682A (en) * | 2017-03-31 | 2018-10-16 | 中国石油化工股份有限公司 | It is a kind of to load the multistage pore canal composite material and preparation method for having TS-1 zeolite membranes |
| CN109433259B (en) * | 2018-10-31 | 2021-12-17 | 中海油天津化工研究设计院有限公司 | Method for in-situ modification of propylene epoxidation catalyst |
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