A process for the production of valeric acid from butene and / or butanol

Abstract

The application discloses a method for preparing valeric acid from butene and / or butanol, and belongs to the field of heterogeneous catalytic conversion. The method comprises the following steps: contacting raw material gas containing butene and / or butanol and CO with a solid acid catalyst, and reacting to obtain valeric acid; and the solid acid catalyst comprises a zeolite molecular sieve. The method has high selectivity of valeric acid; and the performance of the deactivated catalyst does not obviously decrease after multiple resurrections. The application realizes, for the first time, acid-catalyzed conversion of butene or butanol into valeric acid under gas-solid phase conditions through heterogeneous carbonylation, and opens up a new path for preparing high-value-added chemicals from butene and / or butanol through heterogeneous carbonylation.

Description

Technical Field

[0001] This application relates to a method for preparing valeric acid from butene and / or butanol, which belongs to the field of heterogeneous catalytic conversion. Background Technology

[0002] Butene is a secondary product of chemical processes involving petroleum, coal, and natural gas. It is the simplest olefin with isomers, consisting of n-butene (1-butene, 2-butene) and isobutene. Butene has three main uses: as a fuel additive, as a monomer in polymer materials, and as a raw material for fine chemical processing. Due to the presence of isomers, ideally, n-butene and isobutene need to be separated before fine processing. However, because butene isomers are difficult to separate, industrially, unseparated mixed butene is often used directly as a raw material to prepare downstream chemicals, such as tert-butanol (TBA) or methyl tert-butyl ether (MTBE).

[0003] Valeric acid, such as pivalic acid, also known as neovaleric acid or trimethylacetic acid, is a white needle-like crystal at room temperature with a melting point of 35.5℃ and a boiling point of 163.8℃. It is readily soluble in alcohols and ethers but not easily hydrolyzed. Pivalic acid is a very important chemical raw material and reagent, a crucial raw material for organic synthesis, and an important intermediate in pesticides, pharmaceuticals, and dyes. It is also used in high-grade coatings, polymerization initiators, photosensitive materials, and fragrances, making it one of the most widely used alkyl carboxylic acids. Currently, the synthesis method for pivalic acid is a homogeneous reaction catalyzed by a strong liquid acid, resulting in limited production capacity. Pivalic acid is mainly imported, and as of 2023, the market price reached 12,000-20,000 yuan / ton, representing significant potential profits.

[0004] Other valeric acids, such as 2-methylbutyric acid and n-valeric acid, are important food additives, pharmaceutical and flavoring intermediates, and are used in the production of sedative-hypnotic drugs. Summary of the Invention

[0005] This application provides a method for preparing valeric acid, based on mixed butene as a raw material, which can directly generate valeric acid over a catalyst containing zeolite molecular sieves. The method for producing valeric acid provided in this application is a gas-solid phase reaction using a non-precious metal catalyst. The process is simple, the catalyst is readily available and inexpensive, and it has significant industrial application prospects. The catalyst used in this method is free of precious metals and does not require the addition of iodine-containing compounds; the reaction system is a gas-solid phase reaction, the process is simple, and it has broad application prospects.

[0006] A method for preparing valeric acid from butene and / or butanol, the method comprising:

[0007] A feed gas containing butene and / or butanol and CO is contacted with a solid acid catalyst to react and obtain valeric acid.

[0008] The solid acid catalyst includes zeolite molecular sieves;

[0009] The zeolite molecular sieve is selected from at least one of the following: acidic zeolite molecular sieves with MTT structure, acidic zeolite molecular sieves with MEL structure, acidic zeolite molecular sieves with MWW structure, acidic zeolite molecular sieves with FAU structure, acidic zeolite molecular sieves with FER structure, acidic zeolite molecular sieves with MFI structure, acidic zeolite molecular sieves with MOR structure, acidic zeolite molecular sieves with CHA structure, acidic zeolite molecular sieves with BEA structure, and acidic zeolite molecular sieves with TON structure.

[0010] Optionally, the zeolite molecules are screened from at least one of H-ZSM-23 (MTT), H-ZSM-11 (MEL), H-MCM-22 (MWW), Y (FAU), H-ZSM-35 (FER), H-ZSM-5 (MFI), H-MOR, H-SSZ-13 (CHA), beta (BEA), and H-ZSM-22 (TON).

[0011] Optionally, the silicon-to-aluminum atomic ratio of the zeolite molecular sieve is 5 to 120.

[0012] Optionally, the silicon-to-aluminum atomic ratio of the zeolite molecular sieve is independently selected from any value of 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120 or a range between any two.

[0013] Those skilled in the art can prepare acidic zeolite molecular sieves using any suitable method in the prior art, and this application does not limit the preparation method. A preferred method for preparing acidic zeolite molecular sieves is described below: Na-type molecular sieves are placed in a 0.5–1 mol / L NH4NO3 aqueous solution, subjected to ion exchange at room temperature to 90°C for 0.5–10 h, washed with deionized water, and the above steps are repeated 1–3 times. The sieves are then dried at 80–150°C and calcined at 500–600°C to obtain the acidic zeolite molecular sieve.

[0014] Optionally, the zeolite molecular sieve is modified; the modification is metal element modification or silanization modification;

[0015] The metallic element is selected from at least one of Fe, Cu, Zn, Ga, and Ag;

[0016] The silane is selected from at least one of silanes, silicates, and silica sols.

[0017] Optionally, the solid acid catalyst is a shaped acidic zeolite molecular sieve;

[0018] It is obtained by mixing acidic zeolite molecular sieves and matrix, kneading, extruding into strips, drying, and calcining;

[0019] The matrix is ​​selected from at least one of alumina, silicon dioxide, magnesium oxide, and kaolin.

[0020] The mass content of acidic zeolite molecular sieve is 50-100%.

[0021] Optionally, the mass content of the acidic zeolite molecular sieve is independently selected from any value of 50%, 60%, 70%, 80%, 90%, 100%, or a range between any two.

[0022] Those skilled in the art can prepare solid acid catalysts containing a matrix using any suitable method in the prior art, and this application does not limit the preparation method. The following describes a preferred method for preparing a solid acid catalyst containing a matrix: acidic zeolite molecular sieve, matrix, and guar gum powder are mixed in a certain proportion, 10% nitric acid is added and kneaded, the mixture is shaped by extrusion, and calcined at 500-600°C to obtain a solid acid catalyst containing a matrix.

[0023] Optionally, the raw material is unseparated butene and / or butanol.

[0024] Optionally, the butene includes n-butene and isobutene, with a n-to-isobutene ratio of 0-20.

[0025] Preferably, the positive-to-negative ratio is 0-8.

[0026] Optionally, the butene-to-isobutene ratio in the mixed butene is independently selected from any value of 0, 0.5, 1, 2, 4, 8, 16, 20 or a range between any two.

[0027] Optionally, the n-butene includes 1-butene and 2-butene, wherein the ratio of 1-butene to 2-butene is 0-∞.

[0028] Preferably, the ratio of 1-butene to 2-butene is 1-8.

[0029] Optionally, the 1-butene to 2-butene ratio is independently selected from any value of 1, 2, 3, 4, 5, 6, 7, 8 or a range between any two.

[0030] Optionally, the butanol includes n-butanol and isobutanol, with a n-to-iso ratio of 0-20.

[0031] Preferably, the positive-to-negative ratio is 0-6.

[0032] Optionally, the butanol-to-butanol ratio in the butanol is independently selected from any value of 0, 0.5, 1, 2, 4, 8, 16, 20 or a range between any two.

[0033] Preferably, the isobutanol includes sec-butanol, isobutanol, and tert-butanol.

[0034] Optionally, the valeric acid includes tervaeric acid and n-valeric acid.

[0035] Optionally, the molar ratio of CO to butene and / or butanol is 0.05:1 to 100:1;

[0036] Preferably, the molar ratio of CO to butene and / or butanol is 1:1 to 90:1.

[0037] Optionally, the molar ratio of CO to butene and / or butanol is independently selected from any value or a range between 0.05:1, 0.1:1, 0.5:1, 1:1, 2:1, 5:1, 10:1, 20:1, 50:1, 60:1, 80:1, 100:1, 120:1, 150:1, 180:1, and 200:1.

[0038] Optionally, the feed gas also contains water, and the molar ratio of water to butene and / or butanol is 0:1 to 32:1.

[0039] Preferably, the molar ratio of water to butene and / or butanol is 0.05:1 to 25:1.

[0040] Optionally, the molar ratio of water to butene and / or butanol is independently selected from any value or a range between 0.05:1, 0.1:1, 0.1:1, 0.5:1, 1:1, 2:1, 4:1, 5:1, 6:1, 8:1, 10:1, 12:1, 15:1, 16:1, 18:1, 20:1, 22:1, 25:1, 28:1, 30:1, and 32:1.

[0041] Optionally, the raw material gas contains other gases;

[0042] The other gases are selected from at least one of hydrogen, nitrogen, helium, argon, and carbon dioxide;

[0043] The other gases comprise 0 to 50% of the volume of CO gas.

[0044] Optionally, the volume percentage of the other gases in the CO gas is independently selected from any value of 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, or any range between two.

[0045] Optionally, the reaction temperature is 100–300°C.

[0046] Preferably, the reaction temperature is 100-220°C.

[0047] Optionally, the temperature of the reaction is independently selected from any value of 100°C, 100°C, 150°C, 200°C, 250°C, 300°C, or a range between any two.

[0048] Optionally, the reaction pressure is 0.1 to 20 MPa.

[0049] Preferably, the reaction pressure is 2.0 to 15.0 MPa.

[0050] Optionally, the pressure of the reaction is independently selected from any value or a range between 0.1 MPa, 0.2 MPa, 0.5 MPa, 1 MPa, 2 MPa, 5 MPa, 8 MPa, 10 MPa, 12 MPa, 15 MPa, 18 MPa, and 20 MPa.

[0051] Optionally, the mass hourly space velocity (HHSV) of the butene and / or butanol is 0.001–20.0 h⁻¹. -1 .

[0052] Preferably, the mass hourly space velocity (MSV) of the butene and / or butanol is 0.05–10.0 h⁻¹. -1 .

[0053] Optionally, the mass hourly space velocity of butene and / or butanol is independently selected from 0.001 h⁻¹. -1 0.01h -1 0.05h -1 0.1h -1 0.3h -1 0.5h -1 1h -1 1.5h -1 2h -1 3h -1 5h -1 7.5h -1 10h -1 12.5h -1 15h -1 17.5h -1 20.0h -1 Any value in or a range between any two.

[0054] Optionally, the reaction is carried out in a pressure-resistant reactor;

[0055] The reactor includes at least one of a fixed-bed reactor, a fluidized-bed reactor, and a moving-bed reactor.

[0056] Those skilled in the art can select a suitable reactor based on actual production needs. Preferably, the reactor is a fixed-bed reactor.

[0057] The beneficial effects that this application can produce include:

[0058] 1) The method for producing valeric acid provided in this application is the first to achieve the heterogeneous carbonylation conversion of butene or butanol to valeric acid under gas-solid phase conditions, opening up a new route for the preparation of high-value-added chemicals from butene and / or butanol via heterogeneous carbonylation. It can stably, efficiently, and selectively obtain valeric acid, especially pteropenic acid, with correspondingly low energy consumption for production and separation; therefore, this method has broad application prospects.

[0059] 2) The method for producing valeric acid provided in this application has a safe, green and stable catalyst compared with existing methods; the catalyst can be repeatedly regenerated after deactivation without significant decrease in activity; the catalyst production cost is low; there are fewer processing steps; and there is less waste discharge. Attached Figure Description

[0060] Figure 1 The image shows the XRD pattern of the hydrogen-form molecular sieve sample prepared in Example 1. Detailed Implementation

[0061] The present application is described in detail below with reference to the embodiments, but the present application is not limited to these embodiments.

[0062] Unless otherwise specified, the raw materials and catalysts used in the embodiments of this application were all purchased commercially.

[0063] Unless otherwise specified, all test methods are standard and all instrument settings are those recommended by the manufacturer.

[0064] Molecular sieve raw material sources: Some of the molecular sieve raw materials used in the experiment were directly purchased commercially, while others were synthesized based on literature. Specific sources and molecular sieve nomenclature are shown in Table 1. Specifically, in Table 1:

[0065] The synthesis method of Y comes from the literature CUI W, ZHU D, TAN J, et al. Synthesis of mesoporous high-silica zeolite Y and their catalytic cracking performance[J]. Chinese Journal of Catalysis, 2022, 43(7): 1945-54.

[0066] The synthesis method of MOR molecular sieves comes from the literature CAO K, FAN D, ZENG S, et al. Organic-free synthesis of MOR nanoassemblies with excellent DME carbonylation performance[J]. Chinese Journal of Catalysis, 2021, 42(9):1468-77.

[0067] The synthesis method of BETA molecular sieves comes from the literature TAKEWAKI T, HWANG SJ, YAMASHITAH, et al. Synthesis of *BEA-type molecular sieves using mesoporous materials as reagents[J]. Microporous and Mesoporous Materials, 1999, 32(3):265-78.

[0068] The analysis method in the embodiments of this application is as follows:

[0069] The products and unreacted raw materials were analyzed online using an Agilent 7890B gas chromatograph. The FID detector was connected to a PLOT-Q capillary column, and the TCD detector was connected to a Porapak Q packed column.

[0070] In the embodiments of this application, the conversion rate and selectivity are calculated as follows:

[0071] In the examples, the conversion rates of butene and / or butanol were calculated using the internal standard method, and the product selectivity was calculated using the normalization method. Furthermore, under the selected reaction conditions, butanol readily dehydrates to butene; therefore, the conversion rates and product selectivity when using a mixture of butene or butanol as reactants are calculated with butene as the reactant.

[0072] Butene and / or butanol conversion rate = [(number of carbon moles of butene and / or butanol in feed gas) - (number of carbon moles of butene and / or butanol in product)] ÷ (number of carbon moles of butene and / or butanol in feed gas) × (100%)

[0073] Product selectivity = (Number of carbon moles in the product ÷ Total number of carbon moles in the organic matter of the product) × 100%

[0074] Table 1. Sources and silicon-to-aluminum ratios of different catalysts

[0075]

[0076]

[0077] Example 1 Catalyst Preparation

[0078] Preparation of acidic zeolite molecular sieves

[0079] The Na-type molecular sieves in Table 1 were obtained by ion exchange with NH4NO3 and drying and calcining.

[0080] Preparation of HZSM-23: In a hydrothermal synthesis reactor, NaZSM-23 molecular sieve powder was added to a pre-prepared 1 mol / L NH4NO3 aqueous solution at a solid-liquid mass ratio of 1:10. The mixture was stirred and reacted at 80℃ for 2 h. After vacuum filtration and washing with water, the mixture was subjected to three consecutive reaction cycles. The mixture was then dried overnight at 120℃ and calcined at 550℃ for 4 h to obtain the desired catalyst sample HZSM-23.

[0081] The steps for preparing other Na-type molecular sieves into acidic zeolite molecular sieves in Table 1 are the same as the reaction conditions and steps for preparing HZSM-23 molecular sieves from NaZSM-23 molecular sieves; only the corresponding molecular sieve raw materials need to be changed.

[0082] The phase composition of the hydrogen form samples was analyzed using a PANalytical X'Pert PRO X-ray diffractometer (Netherlands). Analysis conditions: Cu and Kα rays were used. Graphite monochromator, Ni filter, tube voltage 40kV, tube current 40mA, scan speed 5° / min, scan area 5-60°. (Attached) Figure 1 The XRD patterns of the hydrogen-form molecular sieves prepared in Example 1, such as ZSM-5, ZSM-35, MCM-22, and ZSM-22, are shown in the attached figures. As can be seen from the attached figures, the hydrogen-form samples all maintained typical characteristic peaks, indicating that the samples were not damaged during the preparation process.

[0083] Preparation of matrix-containing samples

[0084] The matrix-containing molded hydrogen form sample was prepared by extrusion molding.

[0085] This embodiment uses the HZSM-23 (Si / Al=61) sample as an example to prepare a hydrogen form sample containing a matrix. The preparation methods of other hydrogen form molecular sieves in Table 1 are similar to those of the HZSM-23 (Si / Al=61) sample, and will not be described in detail here.

[0086] Preparation of HZSM-23 molecular sieve containing an alumina matrix: 50g of raw material sample HZSM-23 was thoroughly mixed with 50g of alumina, and 10%wt nitric acid was added and kneaded. The kneaded sample was formed into lumps and extruded using an extruder. The extruded sample was dried at 120℃ and calcined at 550℃ for 4h to obtain an acidic zeolite molecular sieve containing a matrix, which was labeled as H(m)-11#.

[0087] Preparation of HZSM-23 molecular sieve containing a mixed matrix of silica, alumina, and magnesium oxide: 80g of HZSM-23 was mixed with 20g of a mixture containing silica, alumina, and magnesium oxide. The mass ratio of silica:alumina:magnesia was 2:2:1. 10% wt nitric acid was added and kneaded. The kneaded sample was then extruded using an extruder. The extruded sample was dried at 120℃ and calcined at 550℃ for 4 hours to obtain an acidic zeolite molecular sieve containing the matrix, labeled H(m)-12#.

[0088] Preparation of HZSM-23 molecular sieve containing kaolin matrix: 80g HZSM-23 and 20g kaolin were mixed. 10% wt nitric acid was added and kneaded. The kneaded sample was extruded into strips using an extruder. The extruded sample was dried at 120℃ and calcined at 550℃ for 4h to obtain an acidic zeolite molecular sieve containing matrix, labeled as H(m)-13#.

[0089] Preparation of HZSM-23 molecular sieve containing a magnesium oxide matrix: 80g of HZSM-23 and 20g of magnesium oxide were mixed. 10% wt nitric acid was added and kneaded. The kneaded sample was extruded into strips using an extruder. The extruded sample was dried at 120℃ and calcined at 550℃ for 4h to obtain an acidic zeolite molecular sieve containing a matrix, labeled as H(m)-14#.

[0090] Preparation of metal-modified samples

[0091] Metal-modified hydrogen-form samples were prepared by impregnation or ion exchange.

[0092] This embodiment uses HZSM-23 (Si / Al=61) and HZSM-35 (Si / Al=79) as representatives to prepare metal-modified hydrogen form samples. The preparation methods of other metal-modified hydrogen form molecular sieves in Table 1 are similar to those of the HZSM-23 (Si / Al=61) sample, and will not be described in detail here.

[0093] Preparation of metal-modified HZSM-23 molecular sieve: 10g of raw material sample HZSM-23 was mixed with 2g of pre-prepared aqueous solutions containing 3wt% of modifying elements Cu(NO3)2, Zn(NO3)2, AgNO3, Fe(NO3)3, and Ga(NO3)3, and stirred until impregnated. The modified sample was dried at 80℃ and calcined at 550℃ for 12h to obtain acidic zeolite molecular sieve containing modified metals, and the sample was labeled H(m)-15-19#.

[0094] Preparation of silanized modified HZSM-23 molecular sieve: 10g of raw material sample HZSM-23 was mixed with 4g of pre-prepared silica sol containing 5wt% Si source, tetrachlorosilane, and an aqueous solution of orthosilicate. Deionized water was added to adjust the solid-liquid ratio to 1:5. The solution was stirred for 2h under water bath heating at 80℃. The modified sample was dried at 80℃ and calcined at 550℃ for 12h to obtain silanized modified acidic zeolite molecular sieve, sample labeled H(m)-20#.

[0095] For zeolite molecular sieves modified with other elements, and for preparing acidic zeolite molecular sieves containing a matrix, the above methods can be used as needed. Typical samples prepared are shown in Table 2.

[0096] Table 2 Sample number and sample composition

[0097]

[0098] Example 2: Preparation of valeric acid by mixing butene on different catalysts

[0099] 1g of each of the solid acid catalysts listed in Table 2 was loaded into a fixed-bed reactor with an inner diameter of 10mm and a quartz tube liner (quartz tube inner diameter 6mm). The temperature was increased to 400℃ at 5℃ / min under a nitrogen atmosphere and maintained for 4 hours. Then, the temperature was lowered to 200℃ under a nitrogen atmosphere, and the pressure of the reaction system was increased to 6MPa using CO. The reactants were passed through the catalyst bed from top to bottom. The mass hourly space velocity (WHSV) of the mixed butene feed was 0.4h⁻¹. -1 The molar ratio of carbon monoxide to mixed butene was 60:1; the molar ratio of water to mixed butene was 1:1; the ratio of normal to isobutene was 2:1, of which the ratio of 1-butene to 2-butene was 1:1; the catalytic reaction was carried out for 8 hours at a reaction temperature of 200℃, and the reaction results are shown in Table 3.

[0100] Table 3. Reaction results on different catalysts

[0101] catalyst Butene conversion rate (%) Valeric acid selectivity (%) other(%) H-1# 48.81 90.42 9.58 H-2# 63.78 39.07 60.93 H-3# 59.36 40.28 59.72 H-4# 50.19 17.66 82.34 H-5# 31.44 57.51 42.49 H-6# 70.99 60.31 39.69 H-7# 34.20 51.54 48.46 H-8# 41.00 11.54 88.46 H-9# 23.05 2.50 97.5 H-10# 10.51 30.19 69.81 H(m)-11# 41.84 88.51 11.49 H(m)-12# 39.44 89.04 10.96 H(m)-13# 37.58 89.07 10.93 H(m)-14# 35.81 89.45 10.55 H(m)-15# 53.65 87.43 12.57 H(m)-16# 54.11 79.05 20.95 H(m)-17# 50.12 72.32 27.68 H(m)-18# 57.62 86.74 13.26 H(m)-19# 57.79 83.86 16.14 H(m)-20# 43.10 93.57 6.43 H-21# 54.61 94.50 5.5 H-22# 39.20 86.68 13.32

[0102] As shown in Table 3, solid acid catalysts based on acidic zeolite molecular sieves can achieve the purpose of producing pentanoic acid and other pentanoic acids from mixed butenes.

[0103] Example 3: Direct conversion of butanol onto different catalysts to prepare valeric acid

[0104] 1g of each of the solid acid catalysts listed in Table 2 was loaded into a fixed-bed reactor with an inner diameter of 10mm and a quartz tube liner (quartz tube inner diameter 6mm). The temperature was increased to 400℃ at 5℃ / min under a nitrogen atmosphere and maintained for 4 hours. Then, the temperature was lowered to 200℃ under a nitrogen atmosphere, and the pressure of the reaction system was increased to 4MPa using CO. The reactants were passed through the catalyst bed from top to bottom. The mass hourly space velocity (WHSV) of the mixed butanol feed was 0.53 h⁻¹. -1 The molar ratio of carbon monoxide to mixed butanol was 60:1; the molar ratio of water to mixed butanol was 1:1; the ratio of normal to isobutanol was 2:1, of which the ratio of sec-butanol to tert-butanol was 1:1; the catalytic reaction was carried out for 8 hours at a reaction temperature of 200℃, and the reaction results are shown in Table 4.

[0105] Table 4. Reaction results on different catalysts

[0106]

[0107]

[0108] As shown in Table 4, solid acid catalysts based on acidic zeolite molecular sieves can achieve the purpose of producing pentanoic acid and other pentanoic acids from mixed butanol. The reactivity of mixed butanol is slightly lower than that of mixed butene, but the product selectivity is similar.

[0109] Tables 3 and 4 show that acidic zeolite molecular sieves can simultaneously catalyze the conversion of butene and butanol into valeric acid.

[0110] Example 4: Direct conversion of butene into pentanoic acid and other pentanoic acids by mixing butene at different reaction temperatures.

[0111] The catalyst used was sample H-1#, and the reaction temperatures ranged from 100 to 250°C. Other reaction conditions were the same as in Example 2. The results of the catalytic reaction after 1 hour are shown in Table 5.

[0112] Table 5. Reaction results at different reaction temperatures.

[0113] Reactor temperature (°C) 100 150 200 250 Butene conversion rate (%) 9.10 22.84 48.81 75.14 Selectivity of pentovalinic acid (%) 1.54 19.21 88.06 28.73 Other valeric acid selectivity (%) 0 0.88 2.36 20.45 Selectivity of other compounds (%) 98.46 79.91 9.58 50.82

[0114] As shown in Table 5, temperature has a significant impact on the preparation of pteropenic acid and other valerates from mixed butenes. As the temperature increases, the conversion rate of mixed butenes increases. However, when the temperature exceeds 200℃, the increase in temperature will promote the formation of a large number of polymeric hydrocarbons, thereby leading to a decrease in the overall selectivity of pteropenic acid and other valerates.

[0115] Example 5: Direct conversion of butene under different reaction pressures to prepare pentylamino acid and other pentylamino acids.

[0116] The catalyst used was sample H-1#, and the reaction pressures were 0.1 MPa, 6 MPa, 10 MPa, and 15 MPa, respectively. Other conditions were the same as in Example 2. The results of the reaction running for 8 hours are shown in Table 6.

[0117] Table 6. Reaction results under different reaction pressures.

[0118] Reaction pressure (MPa) 0.1 6 10 15 Mixed butene conversion rate (%) 6.87 48.81 55.74 70.99 Selectivity of pentovalinic acid (%) 0.30 88.06 87.07 65.91 Other valeric acid selectivity (%) 0 2.36 9.65 26.10 Selectivity of other compounds (%) 99.7 9.58 3.28 7.99

[0119] Table 6 shows that increasing the reaction pressure helps promote the preparation of pivalic acid and other valerates from mixed butenes, and the reaction pressure is directly proportional to the conversion rate of mixed butenes. At low pressure, the product significantly promotes the selectivity of pivalic acid, while at high pressure, it significantly promotes the selectivity of other valerates.

[0120] Example 6: Direct conversion of mixed butenes to prepare pentanoic acid and other pentanoic acids under different mass space velocities of mixed butenes

[0121] Using catalyst sample H-1#, the mass hourly space velocities (HHSVs) of the mixed butene were 0.05, 0.4, 1, and 3.2 h⁻¹. -1 Other conditions were the same as in Example 2, and the results after 8 hours of reaction are shown in Table 7.

[0122] Table 7. Reaction results at different mass space velocities of mixed butenes

[0123] <![CDATA[WHSV of mixed butene (h -1 )]]> 0.05 0.4 1 3.2 Mixed butene conversion rate (%) 54.97 48.81 22.93 9.35 Selectivity of pentovalinic acid (%) 89.41 88.06 87.92 88.01 Other valeric acid selectivity (%) 2.59 2.36 2.41 2.04 Selectivity of other compounds (%) 8 9.58 9.67 9.95

[0124] As shown in Table 7, the higher the catalyst treatment capacity, the lower the conversion rate of mixed butene, while the selectivity of pentylene and other pentylenes is basically unaffected.

[0125] Example 7: Direct conversion of mixed butene to prepare pentanoic acid and other pentanoic acids under different carbon monoxide and mixed butene molar ratios.

[0126] The catalyst used was sample H-1#, and the molar ratios of CO and mixed butene were 0.05, 1, 6, 40, 60 and 90, respectively. Other conditions were the same as in Example 2. The results of the reaction running for 1 hour are shown in Table 8.

[0127] Table 8. Reaction results with different molar ratios of carbon monoxide and mixed butene.

[0128] CO / mixed butene 0.05:1 1:1 6:1 40:1 60:1 90:1 Mixed butene conversion rate (%) 38.01 40.32 41.58 46.39 48.81 49.22 Selectivity of pentovalinic acid (%) 9.28 21.01 30.31 78.52 88.06 78.21 Other valeric acid selectivity (%) 0 0 0 0.99 2.36 11.67 Selectivity of other compounds (%) 90.72 78.99 69.69 20.49 9.58 10.12

[0129] As shown in Table 8, the ratio of carbon monoxide to mixed butene has a significant impact on the conversion of mixed butene; the higher the ratio, the higher the selectivity of pentovalinic acid and other pentovalinic acids.

[0130] Example 8: Direct conversion of butene to prepare pentanoic acid and other pentanoic acids under different water and mixed butene molar ratios.

[0131] The catalyst used was sample H-1#, and the molar ratios of water and mixed butene were 0.5, 1, 2, 4, 8 and 16, respectively. Other conditions were the same as in Example 2. The results of the reaction running for 1 hour are shown in Table 9.

[0132] Table 9. Reaction results with different water and mixed butene molar ratios.

[0133] Water / Mixed Butene 0.5:1 1:1 2:1 4:1 8:1 16:1 Mixed butene conversion rate (%) 47.55 44.32 41.47 35.12 23.11 12.61 Selectivity of pentovalinic acid (%) 77.34 88.06 86.98 78.52 58.06 22.18 Other valeric acid selectivity (%) 2.00 2.36 1.23 0.99 4.53 0.73 Selectivity of other compounds (%) 20.66 9.58 11.79 20.49 37.41 77.09

[0134] As shown in Table 9, the ratio of water to mixed butene has a significant impact on the conversion of mixed butene. An appropriate ratio is beneficial to improving catalyst activity; however, if the ratio is too high, the molecular sieve activity will be significantly reduced.

[0135] Example 9: Direct conversion of butene into pentanoic acid and other pentanoic acids under different molar ratios of n- and isobutene.

[0136] The catalyst used was sample H-1#, and the molar ratios of normal and different butenes were 0.25, 0.5, 1, 2, 4 and 8, respectively. Other conditions were the same as in Example 2. The results of the reaction running for 1 hour are shown in Table 10.

[0137] Table 10 Reaction results for different mixed butene molar ratios

[0138]

[0139]

[0140] As shown in Table 10, the ratio of normal to different types of mixed butene has a significant impact on the conversion rate of mixed butene, but no significant difference in the overall selectivity of the product. This indicates that the carbonylation of mixed butene by molecular sieve catalysis to produce pentanoic acid and other pentanoic acids is universally applicable to mixed butene with different components.

[0141] Example 10: Direct conversion of butene to pivalic acid and other valerates under different 1-butene and 2-butene molar ratios.

[0142] The catalyst used was sample H-1#, and the molar ratios of 1-butene and 2-butene were 0, 1, 2, 4, 8 and ∞, respectively. Other conditions were the same as in Example 2. The results of the reaction running for 1 hour are shown in Table 11.

[0143] Table 11 Reaction results with different molar ratios of carbon monoxide and mixed butene

[0144] 1-Butene:2-Butene 0:1 1:1 2:1 4:1 8:1 1:0 Mixed butene conversion rate (%) 42.03 40.32 40.09 40.55 41.68 40.47 Selectivity of pentovalinic acid (%) 87.95 88.06 88.26 88.00 89.21 87.96 Other valeric acid selectivity (%) 2.36 2.00 3.77 1.90 2.79 2.94 Selectivity of other compounds (%) 9.69 9.94 7.97 10.10 8.00 9.10

[0145] As shown in Table 11, the higher the 1-butene content, the more significant the effect on the molecular sieve activity, but the overall effect is relatively weak.

[0146] Example 11: When the carbon monoxide feed gas contains any one or more of hydrogen, nitrogen, helium, argon, carbon dioxide, etc., the mixed butene is directly converted to prepare pentanoic acid and other pentanoic acids.

[0147] The catalyst used was sample H-1#. Other gases contained in CO are shown in Table 12. Other conditions were the same as in Example 2. The results of the reaction running for 8 hours are shown in Table 12.

[0148] Table 12 Reaction results when carbon monoxide feed gas contains other gases

[0149]

[0150]

[0151] As shown in Table 12, the increase of impurity gases in carbon monoxide directly leads to a decrease in the ratio of carbon monoxide to mixed butenes, and a decrease in the selectivity of pentanoic acid and other pentanoic acids. The presence of hydrogen gas causes a sharp decrease in catalyst activity.

[0152] Example 12: Direct conversion of butene into pentylene and other pentylene acids in different reactors

[0153] The catalyst used was sample H-1#, and the reaction was carried out in fixed bed, fluidized bed and moving bed, respectively. Other conditions were the same as in Example 2. The reaction was run for 8 hours, and the results are shown in Table 13.

[0154] Table 13 Reaction results in different reactors

[0155]

[0156] As shown in Table 13, different reactor types can all achieve the conversion of mixed butenes into pentylene and other pentylenes.

[0157] Example 13 Results of the preparation of valeric acid from butene and butanol after regeneration of the deactivated catalyst in the butene and butanol system.

[0158] The deactivated catalyst of the butene system was regenerated at 550℃ for 12 hours in air. After regeneration, 1 g of the corresponding regenerated catalyst was loaded into a fixed-bed reactor with an inner diameter of 10 mm and a quartz tube liner (quartz tube inner diameter 6 mm). The temperature was increased to 400℃ at 5℃ / min under nitrogen atmosphere and held for 4 hours. Then, the temperature was lowered to 200℃ under nitrogen atmosphere, and the pressure of the reaction system was increased to 6 MPa using CO. The reactants were passed through the catalyst bed from top to bottom. The mass hourly space velocity (HSV) of the mixed butene feed was 0.4 h⁻¹. -1The molar ratio of carbon monoxide to mixed butene was 60:1; the molar ratio of water to mixed butene was 1:1; the ratio of normal to isobutene was 2:1, with the ratio of 1-butene to 2-butene being 1:1; the catalytic reaction was carried out for 8 hours at a reaction temperature of 200℃. The reaction results are shown in Table 14.

[0159] The deactivated catalyst in the butanol system was regenerated at 550°C for 12 hours in air. After regeneration, 1 g of the corresponding regenerated catalyst was loaded into a fixed-bed reactor with an inner diameter of 10 mm and a quartz tube liner (quartz tube inner diameter 6 mm). The temperature was increased to 400°C at 5°C / min under nitrogen atmosphere and held for 4 hours. Then, the temperature was lowered to 200°C under nitrogen atmosphere, and the pressure of the reaction system was increased to 4 MPa using CO. The reactants were passed through the catalyst bed from top to bottom. The mass hourly space velocity (WHSV) of the mixed butanol feed was 0.53 h⁻¹. -1 The molar ratio of carbon monoxide to mixed butanol was 60:1; the molar ratio of water to mixed butanol was 1:1; the ratio of normal to isobutanol was 2:1, with the ratio of sec-butanol to tert-butanol being 1:1; the catalytic reaction was carried out for 8 hours at a reaction temperature of 200℃. The reaction results are shown in Table 14.

[0160] Table 14 Results of catalytic conversion of olefins to carboxylic acids using the corresponding regenerated catalysts

[0161] Regenerated catalyst Material types Material conversion rate (%) Carboxylic acid selectivity (%) Other options (%) H-1#-re Butene 48.24 90.03 9.97 H-1#-re Butanol 44.27 90.56 9.28

[0162] As shown in Table 14, the reactivity of the deactivated catalyst after regeneration is basically the same as that of the fresh catalyst.

[0163] The above description is merely a few embodiments of this application and is not intended to limit this application in any way. Although this application discloses preferred embodiments as described above, it is not intended to limit this application. Any changes or modifications made by those skilled in the art without departing from the scope of the technical solution of this application using the disclosed technical content are equivalent to equivalent implementation cases and fall within the scope of the technical solution.

Claims

1. A method for preparing valeric acid from butene and / or butanol, characterized in that, The method includes: A feed gas containing butene and / or butanol and CO is contacted with a solid acid catalyst to react and obtain valeric acid. The solid acid catalyst includes zeolite molecular sieves; The zeolite molecular sieve is selected from at least one of the following: acidic zeolite molecular sieves with MTT structure, acidic zeolite molecular sieves with MEL structure, acidic zeolite molecular sieves with MWW structure, acidic zeolite molecular sieves with FAU structure, acidic zeolite molecular sieves with FER structure, acidic zeolite molecular sieves with MFI structure, acidic zeolite molecular sieves with MOR structure, acidic zeolite molecular sieves with CHA structure, acidic zeolite molecular sieves with BEA structure, and acidic zeolite molecular sieves with TON structure.

2. The method according to claim 1, characterized in that, The zeolite molecules are selected from at least one of H-ZSM-23, H-ZSM-11, H-MCM-22, Y, H-ZSM-35, H-ZSM-5, H-MOR, H-SSZ-13, beta, and H-ZSM-22. Preferably, the silicon-to-aluminum atomic ratio of the zeolite molecular sieve is 5 to 120.

3. The method according to claim 1, characterized in that, The zeolite molecular sieve has been modified; the modification is metal element modification or silanization modification. The metallic element is selected from at least one of Fe, Cu, Zn, Ga, and Ag; The silane is selected from at least one of silanes, silicates, and silica sols.

4. The method according to claim 1, characterized in that, The solid acid catalyst is a shaped acidic zeolite molecular sieve. It is obtained by mixing acidic zeolite molecular sieves and matrix, kneading, extruding into strips, drying, and calcining; The matrix is ​​selected from at least one of alumina, silicon dioxide, magnesium oxide, and kaolin. The mass content of acidic zeolite molecular sieve is 50-100%.

5. The method according to claim 1, characterized in that, The butene includes n-butene and isobutene, with a n-to-isobutene ratio of 0-20; Preferably, the positive-to-negative ratio is 0-8; Preferably, the n-butene comprises 1-butene and 2-butene, and the ratio of 1-butene to 2-butene is 0-∞; Preferably, the ratio of 1-butene to 2-butene is 1-8; Preferably, the butanol comprises n-butanol and isobutanol, with a n-to-isobutanol ratio of 0-20; Preferably, the positive-to-negative ratio is 0-6; Preferably, the isobutanol includes sec-butanol, isobutanol, and tert-butanol.

6. The method according to claim 1, characterized in that, The valeric acid includes tervaeric acid and n-valeric acid.

7. The method according to claim 1, characterized in that, The molar ratio of CO to butene and / or butanol is 0.05:1 to 100:1; Preferably, the molar ratio of CO to butene and / or butanol is 1:1 to 90:1; Preferably, the raw gas also contains water, and the molar ratio of water to butene and / or butanol is 0:1 to 32:1; Preferably, the molar ratio of water to butene and / or butanol is 0.05:1 to 25:1; Preferably, the raw material gas also contains other gases; The other gases are selected from at least one of hydrogen, nitrogen, helium, argon, and carbon dioxide; The other gases comprise 0 to 50% of the volume of CO gas.

8. The method according to claim 1, characterized in that, The reaction temperature is 100–300°C; Preferably, the reaction temperature is 100-220℃; Preferably, the reaction pressure is 0.1–20 MPa; Preferably, the reaction pressure is 2.0 to 15.0 MPa.

9. The method according to claim 1, characterized in that, The mass hourly space velocity (HSV) of the butene and / or butanol is 0.001–20.0 h⁻¹. -1 ; Preferably, the mass hourly space velocity (MSV) of the butene and / or butanol is 0.05–10.0 h⁻¹. -1 .

10. The method according to claim 1, characterized in that, The reaction is carried out in a pressure-resistant reactor; The reactor includes at least one of a fixed-bed reactor, a fluidized-bed reactor, and a moving-bed reactor.

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