CN115869994A - Pd-Ni-Co/NaOH-Hbeta catalyst, and preparation method and application thereof - Google Patents
Pd-Ni-Co/NaOH-Hbeta catalyst, and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 74
- 229910017709 Ni Co Inorganic materials 0.000 title claims abstract description 42
- 229910003267 Ni-Co Inorganic materials 0.000 title claims abstract description 42
- 229910003262 Ni‐Co Inorganic materials 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 claims abstract description 68
- 238000006243 chemical reaction Methods 0.000 claims abstract description 51
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- 239000000243 solution Substances 0.000 claims abstract description 25
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- GWHJZXXIDMPWGX-UHFFFAOYSA-N 1,2,4-trimethylbenzene Chemical compound CC1=CC=C(C)C(C)=C1 GWHJZXXIDMPWGX-UHFFFAOYSA-N 0.000 claims description 20
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 16
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 11
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical group [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 8
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 7
- 229910002094 inorganic tetrachloropalladate Inorganic materials 0.000 claims description 7
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical group [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 7
- 229910052700 potassium Inorganic materials 0.000 claims description 7
- 239000011591 potassium Substances 0.000 claims description 7
- 230000004913 activation Effects 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 230000009467 reduction Effects 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 238000007654 immersion Methods 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 238000004939 coking Methods 0.000 abstract description 5
- 230000008021 deposition Effects 0.000 abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 230000002401 inhibitory effect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 43
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- 229910021536 Zeolite Inorganic materials 0.000 description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000010457 zeolite Substances 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
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- 230000036961 partial effect Effects 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
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- 239000002841 Lewis acid Substances 0.000 description 2
- 229910002808 Si–O–Si Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
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- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a Pd-Ni-Co/NaOH-H beta catalyst and a preparation method and application thereof, wherein the catalyst takes an H beta molecular sieve as a carrier, is modified by NaOH and then loads Pd, ni and Co, and the preparation method of the catalyst comprises the following steps: (1) Activating the H beta molecular sieve, mixing with NaOH solution, heating for reaction, cooling, washing with water, filtering, drying, and placing the obtained solid in NH 4 Carrying out ion exchange and suction filtration in a Cl solution, drying, grinding and activating to obtain NaOH-Hbeta; (2) Soaking NaOH-Hbeta in mixed solution containing nickel salt, cobalt salt and palladium salt in equal volume, standing, drying, grinding, and performingActivating and reducing to obtain the Pd-Ni-Co/NaOH-H beta catalyst which can be used for catalyzing the isomerization reaction of the hemimellitene. The Pd-Ni-Co/NaOH-Hbeta catalyst prepared by using Pd as a carbon deposition inhibiting component and Ni and Co as auxiliary active components not only keeps the high stability of the traditional microporous molecular sieve, but also has higher conversion rate and anti-coking capability, and can effectively prolong the service life of the catalyst.
Description
Technical Field
The invention relates to a catalyst, a preparation method and application thereof, in particular to a Pd-Ni-Co/NaOH-Hbeta catalyst, and a preparation method and application thereof.
Background
The pseudocumene is the main component of reformed aromatic hydrocarbon product, its content is about 35% -40%, and it can be purified to above 99% by adopting conventional rectification method, so that most of pseudocumene in industry can be obtained by separation, and the research on pseudocumene is mainly focused on the aspect of synthesizing other important industrial raw material from pseudocumene. Mesitylene is C 9 The component with the highest added value in the aromatic hydrocarbon has wide industrial application, is widely applied to departments of electronics, aviation, printing and dyeing, mechanical manufacturing and the like, and is a fine chemical raw material with great market prospect. C is rich in the world 9 If the aromatic hydrocarbon can fully utilize the part of precious resources, not only the economic benefit of the oil refining industry is promoted, but also the development of the fine chemical industry in China can be promoted. The method for producing the pseudocumene and the mesitylene reported by domestic and foreign documents mainly comprises the following steps: HF-BF 3 Solvent separation, extractive distillation, isomerization, alkylation and the like. In some current researches on trimethylbenzene isomerization, high-purity pseudocumene is mostly used as a raw material and mordenite is used as a catalyst, but the mixed C is not used 9 H beta molecular sieve shows relatively high catalytic performance in the isomerization reaction of the mesitylene; but with the generation of a large amount of by-products, the catalyst is rapidly coked and deactivated, and further application of the catalyst in industry is limited. Therefore, the development of the mesoporous microporous molecular sieve with higher conversion rate and coking resistance and prolonged service life of the catalyst has important industrial application value.
In some studies on trimethylbenzene isomerization, aluminum trichloride, HM and WO 3 /ZrO 2 Shows lower mesitylene yield of about 14%, 21.55% and 18.7%, respectively. The H beta molecular sieve shows relatively high yield of the partial mesitylene and mesitylene, and is considered as an effective catalyst for the isomerization reaction of the hemimellitene. However, the unique microporous structure of commercial H beta zeolite suggests that the acidic sites inside the channels cannot be fully utilized due to diffusion limitation, low hemimellitene activity is exhibited at low temperature, andthe macromolecule byproducts can not diffuse out of the pore channels in time, which can cause rapid coking and inactivation of the catalyst, and limit further application of the catalyst in industry.
In the article of Suntao et al, the mixed trimethylbenzene is used as raw material and Ni-Mo/HM is used as catalyst, and the reaction temperature is 280 deg.C, reaction pressure is 1.2MPa and mass space velocity is 1.0h -1 And the mixed trimethylbenzene isomerization reaction is carried out under the condition of hydrogen-oil ratio of 6, the conversion rate of the hemimellitene is 77.76 percent, and the total selectivity and the total yield of the pseudomellitene and the mesitylene are 72.93 percent and 56.71 percent respectively.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a Pd-Ni-Co/NaOH-H beta catalyst with good catalytic effect, and also provides a preparation method and application of the Pd-Ni-Co/NaOH-H beta catalyst.
The technical scheme is as follows: the Pd-Ni-Co/NaOH-H beta catalyst takes an H beta molecular sieve as a carrier, and is modified by NaOH to load Pd, ni and Co, wherein the mass ratio of Pd, ni and Co is 0.4-0.6.
The preparation method of the Pd-Ni-Co/NaOH-Hbeta catalyst comprises the following steps:
(1) Activating the H beta molecular sieve, mixing with NaOH solution, heating for reaction, cooling, washing with water, filtering, drying, and placing the obtained solid in NH 4 Carrying out ion exchange and suction filtration in a Cl solution, drying and grinding after full reaction, and then carrying out activation treatment to obtain the micro-mesoporous H beta molecular sieve NaOH-H beta;
(2) Soaking NaOH-H beta in a mixed solution containing nickel salt, cobalt salt and palladium salt in the same volume, standing, drying, grinding, activating, and reducing to obtain the Pd-Ni-Co/NaOH-H beta catalyst.
Further, in the step (1), the solid-to-liquid ratio of the H beta molecular sieve to the NaOH solution is 1g and is 10-30ml, the heating reaction temperature is 60-70 ℃, and the time is 0.1-1H; NH (NH) 4 The concentration of the Cl solution is 0.1-1mol/L, and the temperature of ion exchange is 50-60 ℃.
Further, in the step (2), the nickel-containing salt is nickel nitrate, the cobalt-containing salt is cobalt nitrate, the palladium-containing salt is potassium tetrachloropalladate, and the mass ratio of NaOH-H beta, nickel nitrate, cobalt nitrate and potassium tetrachloropalladate is (5); soaking for 12-24h at the same volume, standing at 50-60 deg.C for 4-8h; the conditions of the reduction treatment were: reducing in hydrogen atmosphere at a hydrogen rate of 10-15ml/min for 2-6h at a temperature of 350-550 ℃.
Further, in the step (1) and the step (2), the conditions of the activation treatment are as follows: the activation temperature is 500-600 ℃, the activation time is 3-5h, and the drying conditions are as follows: drying at 100-120 deg.C for 8-12 hr.
The application of the Pd-Ni-Co/NaOH-H beta catalyst in hemimellitene isomerization reaction comprises the following steps: by mixing C 9 The concentrated hemimellitene solution is used as a reaction raw material, is mixed with Pd-Ni-Co/NaOH-H beta catalyst together with hydrogen after being preheated for isomerization reaction, and is separated from gas and liquid after the isomerization reaction is finished, thus obtaining the hemimellitene.
Further, the mixing of C 9 The hemimellitene enrichment solution comprises the following components: 9.82-10.54% of pseudocumene, 37.49-39.84% of hemimellitene and 49.62-50.91% of heavy components, wherein the conditions of the isomerization reaction are as follows: the reaction temperature is 290-310 ℃, the reaction pressure is 1.3-1.8MPa, and the mass space velocity of the reaction raw materials is 0.6-1.4h -1 And the hydrogen-oil ratio is 8-12.
The invention principle is as follows: in the preparation method, the process of alkali treatment is adopted, and the Si-O-Si and Si-O-Al bonds in the H beta zeolite are damaged due to alkali treatment desilication, so that the H beta zeolite generates a mesoporous structure, the framework aluminum in the original structure is converted into non-framework aluminum, and more acid sites are generated. When metal ions are further adopted for treatment, palladium plays a role in cracking byproducts, the catalyst is prevented from coking, the service life of the catalyst is prolonged, cobalt is used for reducing Lewis acid sites, and the dispersion degree of cobalt and palladium is increased due to the addition of nickel. With hemimellitene reactant on the outer surface of the molecular sieve and in the interior of the pore channel
Reaction at the acid site, generalProtonation of the polyalkylbenzene molecule realizes the transfer of 1, 2-alkyl in the benzene ring, and the isomerized product diffuses out from the pore canal. Therefore, the increase of acid sites and the reduction of Lewis acid sites are beneficial to increase the isomerization selectivity of hemimellitene and reduce the occurrence of side reactions such as disproportionation and the like.
Has the advantages that: compared with the prior art, the invention has the following remarkable advantages:
(1) The mesoporous metal Pd-Ni-Co/NaOH-H beta catalyst prepared by the method not only keeps the high stability of the traditional microporous molecular sieve, but also has higher conversion rate and anti-coking capability, effectively prolongs the service life of the catalyst, and has certain industrial application value;
(2) The preparation method of the catalyst is simple and has strong operability;
(3) The invention takes Pd-Ni-Co/NaOH-Hbeta catalyst as mixed C 9 The hemimellitene in the catalyst is used for isomerization reaction, the catalytic efficiency is high, and the service life is long.
Drawings
FIG. 1 is a diagram of the elemental distribution of a Pd-Ni-Co/NaOH-H β catalyst prepared in example 1 of the present invention;
FIG. 2 is an elemental distribution diagram of an H β molecular sieve of comparative example 1 of the present invention;
FIG. 3 is an elemental distribution plot of a NaOH-Hbeta catalyst prepared according to comparative example 2 of the present invention;
FIG. 4 is an infrared spectrum of catalysts prepared in example 1, comparative example 1 and comparative example 2 of the present invention;
FIG. 5 is a drawing showing adsorption-desorption of nitrogen gas of the catalysts obtained in example 1, comparative example 1 and comparative example 2 of the present invention;
FIG. 6 is a graph showing the pore size distribution of the catalysts obtained in example 1, comparative example 1 and comparative example 2 of the present invention;
FIG. 7 is a comparative XRD pattern of the catalysts prepared in example 1 of the present invention, comparative example 1 and comparative example 2;
FIG. 8 is a trend chart of the life test results of the Pd-Ni-Co/NaOH-H β catalyst in example 8 of the present invention.
Detailed Description
The technical solution of the present invention is further explained below with reference to the examples and the accompanying drawings.
Example 1: the preparation method of the Pd-Ni-Co/NaOH-Hbeta catalyst comprises the following steps:
(1) Activating H beta molecular sieve at 550 ℃ for 4H, mixing with 0.2mol/L NaOH solution according to a solid-to-liquid ratio of 1g 4 Carrying out ion exchange for 1H and suction filtration in a Cl solution, repeating the operation for 4 times, washing at normal temperature until no chloride ions are contained, then drying at 110 ℃ for 10H, grinding into powder, placing in a muffle furnace, and carrying out activation treatment at 550 ℃ for 4H to obtain the micro-mesoporous H beta molecular sieve NaOH-H beta;
(2) Soaking 5g of NaOH-H beta in a mixed solution containing 0.12386g of nickel nitrate, 0.2469g of cobalt nitrate and 0.092g of potassium tetrachloropalladate in an equal volume for 12H, standing at 60 ℃ for 4H, drying at 110 ℃ for 10H to obtain a solid, grinding into powder, activating in a muffle furnace at 550 ℃ for 4H, and reducing in a hydrogen atmosphere at a hydrogen rate of 15ml/min for 4H at a reduction temperature of 420 ℃ to obtain the Pd-Ni-Co/NaOH-H beta catalyst, wherein the element distribution diagram is shown in FIG. 1, and the mass percentages of local O, si, al, co, ni and Pd are 50.6.
Comparative example 1: the element distribution of the untreated H beta molecular sieve is shown in figure 2, and the mass percentages of O, si and Al are 59.9.
Comparative example 2: the difference from example 1 is that: the method does not comprise the step (2), the prepared material is a micro-mesoporous H beta molecular sieve NaOH-H beta, the element distribution is shown in figure 3, and the mass percentages of O, si and Al are as follows, namely, 57.8.
Comparative example 3: the difference from example 1 is that: in the step (2), naOH-H beta is immersed in a solution containing only nickel nitrate in the same volume.
Comparative example 4: the difference from example 1 is that: in the step (2), naOH-H beta is immersed in a solution containing only cobalt nitrate in the same volume.
Comparative example 5: the difference from example 1 is that: in the step (2), the NaOH-H beta is dipped into the solution only containing the potassium tetrachloropalladate in the same volume.
Comparative example 6: the difference from example 1 is that: in the step (2), the NaOH-H beta is dipped in a solution only containing cobalt nitrate and potassium tetrachloropalladate in equal volume.
Comparative example 7: the difference from example 1 is that: in the step (2), the NaOH-H beta is dipped in the solution only containing the nickel nitrate and the cobalt nitrate in the same volume.
Example 2: the Pd-Ni-Co/NaOH-H beta catalyst prepared in the example 1 is used in hemimellitene isomerization reaction, and the steps are as follows: by mixing C 9 In the method, hemimellitene enrichment solution is used as a reaction raw material, is preheated to 293 ℃, is mixed with hydrogen and 1.65g of Pd-Ni-Co/NaOH-H beta catalyst together for isomerization reaction, the isomerization reaction temperature is 290 ℃, the pressure is 1.8MPa, and the mass space velocity of the raw material is 1.0H -1 And after the reaction is finished, carrying out gas-liquid separation, collecting an isomerization product, and detecting by adopting GC7700 gas-phase hydrogen flame chromatography.
Comparative example 8: the difference from example 2 is that the catalysts used were the catalysts prepared in comparative examples 3 to 7.
FIG. 4 shows that three catalysts of H beta, naOH-H beta and Pd-Ni-Co/NaOH-H beta are in the range of 1800-400cm -1 Infra-red spectrogram in the range of 1236-1093cm -1 The absorption peak between them is the asymmetric stretching vibration peak of the internal tetrahedron, 806cm -1 The nearby absorption peak is the symmetric stretching vibration peak of Si-O-Si bond, 577cm -1 And 525cm -1 The nearby absorption peaks are vibration peaks of a framework double four-membered ring and a framework double five-membered ring respectively, compared with the H beta molecular sieve, the positions of characteristic peaks in NaOH-H beta and Pd-Ni-Co/NaOH-H beta samples are not changed, which shows that desiliconization modification does not affect the crystal phase structure of the H beta molecular sieve, but the framework structure is damaged to a certain extent.
FIGS. 5 and 6 are nitrogen adsorption-desorption curves and pore size distribution curves for H β, naOH-H β, pd-Ni-Co/NaOH-H β. As can be seen from fig. 5, the isotherm of H β is in the low pressure region, the adsorption curve rises rapidly, and adsorption within the micropores occurs, showing a typical type I isotherm, demonstrating the microporous structure of the H β sample. Meanwhile, H4-type hysteresis loops attributed to narrow slit-type pores were observed at P/P0>0.5, indicating that irregular pore voids existed between H β particles. The adsorption and desorption curves of the NaOH-H beta sample in the low P/P0 area are overlapped, and sudden rise occurs, so that an H4 type hysteresis loop gradually appears, which indicates that micropores and mesopores exist in the sample, and the generation of the mesopores is attributed to the removal of framework silicon, so that a framework cavity is formed. The Pd-Ni-Co/NaOH-H beta sample still maintains the similar characteristics of the NaOH-H beta sample, and as can be seen from the pore size distribution diagram in FIG. 6, the NaOH-H beta and Pd-Ni-Co/NaOH-H beta samples have more mesopores than the H beta molecular sieve, and the pore size range of the mesopores is concentrated between 2 and 10nm, but the pore size and the pore volume are slightly smaller than those of the NaOH-H beta sample due to the influence of the load of Pd, ni and Co on the pore size and the pore volume of the samples.
FIG. 7 is an XRD spectrum of three catalysts, H beta, naOH-H beta and Pd-Ni-Co/NaOH-H beta. As can be seen from fig. 7, the characteristic H β diffraction peaks appear for all three samples at diffraction angles around 2 θ =7.8 ° and 22.4 °, indicating that the NaOH solution treatment did not change the crystal structure of the H β molecular sieve. The diffraction peak intensity reflects the integrity of the crystal structure of the molecular sieve, and the diffraction peak intensity of NaOH-H beta is reduced compared with H beta, which shows that the NaOH solution has desiliconization effect after treatment, and has certain destructive effect on framework silicon, thereby reducing the crystallinity of the sample. The positions of characteristic diffraction peaks of PdO, niO, and CoO were around 2 θ =33.8 °, 43 °, and 54 °, respectively, while no relevant diffraction peaks were present in Pd-Ni-Co/NaOH-H β, which may be caused by a low metal loading amount or because the supported metal was uniformly dispersed on the surface of the catalyst without forming metal clusters.
The results of the measurements of example 2 and comparative example 8 are shown in table 1, and H β zeolite itself has better catalytic activity for hemimellitene isomerization reaction, but the activity of the catalyst is rapidly decreased as the reaction time is prolonged, and in order to improve the service life of the catalyst, H β zeolite is first treated with alkali and then a carbon deposition inhibiting metal component is added. Ni and Pd have hydrogenation function, and can better inhibit the deposition of coke on the catalyst in the presence of hydrogen. And Co can reduce Lewis sites on the surface of the catalyst and reduce the generation of byproducts. Therefore, when the Ni content is 0.5%, the Co content is 1.0% and the Pd content is 0.6%, the Pd-Ni-Co/NaOH-H beta catalyst has good catalytic activity on the isomerization of the hemimellitene into the pseudocumene and the mesitylene, so that the hemimellitene conversion rate can reach 89.18%, and the total yield of the pseudocumene and the mesitylene can reach 64.50%.
TABLE 1 catalysts obtained in example 1 and comparative examples 3 to 7
Example 3: the difference from example 2 is that the isomerization temperature was 310 ℃.
Example 4: the difference from example 2 is that the pressure of the isomerization reaction was 1.3MPa.
Example 5: the difference from example 2 is that the mass space velocity of the feedstock is 0.6h -1 。
Example 6: the difference from example 2 is that the mass space velocity of the feedstock is 1.4h -1 。
Comparative example 9: the difference from example 2 is that the isomerization temperature was 270 ℃.
Comparative example 10: the difference from example 2 is that the isomerization temperature was 330 ℃.
Comparative example 11: the difference from example 2 is that the isomerization temperature was 350 ℃.
Comparative example 12: the difference from example 2 is that the pressure of the isomerization reaction was 0.3MPa.
Comparative example 13: the difference from example 2 is that the pressure of the isomerization reaction is 0.8MPa.
Comparative example 14: the difference from example 2 is that the pressure of the isomerization reaction is 2.3MPa.
Comparative example 15: the difference from example 2 is that the mass space velocity of the feedstock is 1.8h -1 。
Comparative example 16: the difference from example 2 is that the mass space velocity of the feedstock is 2.2h -1 。
The results obtained in examples 2 to 6 and comparative examples 9 to 16 are summarized in tables 2 to 4.
As can be seen from Table 2, different reaction temperatures have a great influence on the activity of the Pd-Ni-Co/NaOH-H beta catalyst, and the conversion rate of the hemimellitene is continuously increased along with the increase of the reaction temperature, but the overall selectivity and the overall yield of the hemimellitene and the mesitylene are not good; and the higher reaction temperature is easy to cause the acceleration of carbon deposition of the catalyst, which leads to the reduction of the activity of the Pd-Ni-Co/NaOH-Hbeta catalyst, so the more suitable reaction temperature for the reaction is 290-310 ℃ in comprehensive consideration.
TABLE 2 summary of hemimellitene conversion and partial, mesitylene selectivities and yields for the catalysts prepared in examples 2-3 and comparative examples 9-11
| Reaction temperature/. Degree.C | Conversion rate/% | Selectivity/%) | Yield/% | |
| Comparative example 9 | 270 | 77.37 | 72.34 | 55.97 |
| Example 2 | 290 | 89.26 | 72.27 | 64.51 |
| Example 3 | 310 | 92.14 | 56.76 | 52.30 |
| Comparative example 10 | 330 | 92.40 | 54.45 | 50.31 |
| Comparative example 11 | 350 | 93.19 | 46.32 | 43.16 |
As can be seen from Table 3, the different reaction pressures have less influence on the activity of the Pd-Ni-Co/NaOH-H β catalyst. In the pressure range of 0.3-2.3MPa, when the pressure is more than 1.8MPa, the conversion rate of hemimellitene and the yield of mesitylene are hardly influenced by the pressure and are kept stable. From the chemical balance point of view, the isomerization reaction of the hemimellitene is equimolecular reaction, and the number of molecules before and after the reaction is not changed, so the reaction pressure has little influence on the isomerization reaction of the hemimellitene. However, in the reaction process, the reaction pressure has a large influence on side reactions such as disproportionation reaction and the like, and a higher reaction pressure causes energy waste in the operation process, so that the reaction pressure is more suitable for the reaction and is 1.3-1.8MPa in comprehensive consideration.
TABLE 3 summary of hemimellitene conversion and partial and mesitylene selectivities and yields for the catalysts obtained in example 2, example 4 and comparative examples 12 to 14
| Reaction pressure/MPa | Conversion rate/%) | Selectivity/%) | Yield/% | |
| Comparative example 12 | 0.3 | 81.72 | 70.93 | 57.96 |
| Comparative example 13 | 0.8 | 89.52 | 67.64 | 60.55 |
| Example 4 | 1.3 | 90.36 | 70.87 | 64.04 |
| Example 2 | 1.8 | 89.26 | 72.27 | 64.51 |
| Comparative example 14 | 2.3 | 88.71 | 71.68 | 63.59 |
As can be seen from Table 4, the difference in the mass space velocity of the feedstock has a greater effect on the activity of the Pd-Ni-Co/NaOH-H β catalyst. With the increase of the mass airspeed of the raw materials, the reaction residence time is reduced, so that the conversion rate of the hemimellitene and the total yield of the pseudomellitene and the mesitylene are gradually reduced; therefore, the mass space velocity of the reaction is more suitable for 0.6-1.4h -1 。
TABLE 4 summary of hemimellitene conversion and partial, mesitylene selectivities and yields for the catalysts obtained in example 2, example 5 to example 6 and comparative example 15 to comparative example 16
| Mass space velocity/h -1 | Conversion rate/% | Selectivity/%) | Yield/% | |
| Example 5 | 0.6 | 89.05 | 70.29 | 62.60 |
| Example 2 | 1.0 | 89.26 | 72.27 | 64.51 |
| Example 6 | 1.4 | 81.21 | 74.54 | 60.53 |
| Comparative example 15 | 1.8 | 75.04 | 76.68 | 57.54 |
| Comparative example 16 | 2.2 | 71.82 | 77.93 | 55.97 |
Example 7: life investigation experiment of Pd-Ni-Co/NaOH-H beta catalyst
The Pd-Ni-Co/NaOH-Hbeta catalyst pair prepared in example 1 was used for mixing C 9 The continuous catalytic reaction of the concentrated hemimellitene solution in the aromatic hydrocarbon solvent oil is carried out for 25-200H, and as can be seen from figure 8, the activity and the selectivity of the Pd-Ni-Co/NaOH-H beta catalyst are relatively stable along with the continuous increase of the reaction time in the whole experiment, which shows thatThe catalyst has higher catalytic activity and simultaneously has considerable service life.
Claims (10)
1. The Pd-Ni-Co/NaOH-H beta catalyst is characterized in that an H beta molecular sieve is used as a carrier of the catalyst, and Pd, ni and Co are loaded after the H beta molecular sieve is modified by NaOH.
2. The Pd-Ni-Co/NaOH-H β catalyst according to claim 1, characterized in that the mass ratio of Pd, ni and Co is 0.4-0.6-0.8-1.2.
3. A method for preparing the Pd-Ni-Co/NaOH-H β catalyst of claim 1, comprising the steps of:
(1) Activating the H beta molecular sieve, mixing with NaOH solution, heating for reaction, cooling, washing with water, filtering, drying, and placing the obtained solid in NH 4 Carrying out ion exchange and suction filtration in a Cl solution, drying and grinding after full reaction, and then carrying out activation treatment to obtain the micro-mesoporous H beta molecular sieve NaOH-H beta;
(2) Soaking NaOH-H beta in a mixed solution containing nickel salt, cobalt salt and palladium salt in the same volume, standing, drying, grinding, activating, and reducing to obtain the Pd-Ni-Co/NaOH-H beta catalyst.
4. The preparation method of claim 3, wherein in the step (1), the solid-to-liquid ratio of the H beta molecular sieve to the NaOH solution is 1 g.
5. The preparation method according to claim 3, wherein in the step (2), the nickel-containing salt is nickel nitrate, the cobalt-containing salt is cobalt nitrate, the palladium-containing salt is potassium tetrachloropalladate, and the mass ratio of NaOH-H β, nickel nitrate, cobalt nitrate to potassium tetrachloropalladate is 5.
6. The method according to claim 3, wherein in the step (2), the time for the equal-volume immersion is 12-24h; standing at 50-60 deg.C for 4-8 hr; the conditions of the reduction treatment were: reducing in hydrogen atmosphere at a hydrogen rate of 10-15ml/min for 2-6h at a temperature of 350-550 ℃.
7. Use of the Pd-Ni-Co/NaOH-H β catalyst of claims 1-6 in mesitylene isomerization reactions.
8. The application according to claim 7, characterized in that the steps of said application are as follows: by mixing C 9 The concentrated hemimellitene solution is used as a reaction raw material, is preheated and then mixed with hydrogen together with a Pd-Ni-Co/NaOH-H beta catalyst for isomerization reaction, and is subjected to gas-liquid separation after the isomerization reaction is finished, so that the catalyst is obtained.
9. Use according to claim 8, characterized in that the mixture C is 9 The hemimellitene enrichment solution comprises the following components: 9.82 to 10.54 percent of pseudocumene, 37.49 to 39.84 percent of hemimellitene and 49.62 to 50.91 percent of heavy components.
10. Use according to claim 8, wherein the isomerization conditions are: the reaction temperature is 290-310 ℃, the reaction pressure is 1.3-1.8MPa, and the mass space velocity of the reaction raw materials is 0.6-1.4h -1 And the hydrogen-oil ratio is 8-12.
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| CN117101713B (en) * | 2023-10-25 | 2024-01-19 | 南京师范大学 | MnO (MnO) 2 -ZrO 2 /OH - -H beta metal solid acid catalyst, preparation method and application thereof |
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