Process for preparing carboxylic acid from olefin and / or alcohol
Patent Information
- Authority / Receiving Office
- WO · WO
- Patent Type
- Applications
- Current Assignee / Owner
- DALIAN INSTITUTE OF CHEMICAL PHYSICS CHINESE ACADEMY OF SCIENCES
- Filing Date
- 2024-11-29
- Publication Date
- 2026-06-04
Smart Images
Figure CN2024135692_04062026_PF_FP_ABST
Abstract
Description
A method for preparing carboxylic acids from olefins and / or alcohols Technical Field
[0001] This application relates to a method for preparing carboxylic acids from olefins and their alcohols, belonging to the field of catalytic synthesis. Background Technology
[0002] Polyolefins, typically secondary products from chemical processes involving petroleum, coal, and natural gas, are characterized by their isomerism; for example, butene exists in the form of n-butene (1-butene, 2-butene) and isobutene. The main uses of polyolefins are threefold: first, as fuel additives; second, as monomers in polymer materials; and third, as raw materials for fine chemical processing. A significant amount of polyolefins is used for hydration to prepare various polyols. Due to the presence of isomers, it is usually necessary to separate these isomers before fine processing. Because the boiling points and relative volatility of different polyolefin isomers are very similar, separation is difficult, hindering fine processing.
[0003] C5-C9 carboxylic acids are important organic acids and key chemical raw materials. For example, pentylene acid, also known as neopentylene acid or trimethylacetic acid, is a crucial chemical raw material and reagent, an important raw material for organic synthesis, and a vital intermediate in pesticides, pharmaceuticals, and dyes. It is used in high-grade coatings, polymerization initiators, photosensitive materials, and fragrances, making it one of the most widely used alkyl carboxylic acids. C5-C9 carboxylic acids can also undergo many chemical reactions. When the hydroxyl group in the carboxyl group is replaced by other atomic groups, carboxylic acid derivatives are formed, mainly including carboxylic acid esters, acyl halides, acid anhydrides, and amides. Among these, the corresponding carboxylic acid esters are also important fragrances, food additives, and pharmaceutical intermediates.
[0004] Liquid acid-catalyzed carbonylation of olefins and alcohols to produce carboxylic acids is one of the main industrial methods for obtaining carboxylic acids. Its main advantage is that it does not require the use of precious metals, but its disadvantages are also significant: strong liquid acids are highly corrosive, catalysts and products are difficult to separate under homogeneous conditions, and the reaction scale is relatively small. Therefore, developing new technologies for the carbonylation of olefins and alcohols to produce carboxylic acids using solid acid catalysis has important theoretical and practical value. Summary of the Invention
[0005] This application provides a method for preparing carboxylic acids from C4-C8 olefins and their alcohols. The method involves reacting a feed gas containing C4-C8 olefins and their alcohols with a feed gas containing water in contact with a solid acid catalyst to obtain carboxylic acids. The method 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 carboxylic acids from olefins and their alcohols, the method comprising:
[0007] A feed gas containing olefins and their alcohols, CO, and a solid acid catalyst is contacted and reacted to yield carboxylic acids.
[0008] The olefins and their alcohols are selected from at least one of C4-C8 olefins and C4-C8 alcohols;
[0009] The solid acid catalyst includes zeolite molecular sieves.
[0010] Optionally, the C4 olefin is selected from at least one of 1-butene, 2-butene, and isobutene; the C4 alcohol is selected from at least one of n-butanol, isobutanol, and tert-butanol.
[0011] C4 + The olefin is selected from at least one of pentene, hexene, hepten, and octene; C4 + The alcohol is selected from at least one of pentanol, hexanol, heptanol, and octanol.
[0012] Among them, 1-butene and 2-butene are n-butene.
[0013] Optionally, when the olefin and its alcohol are C4 olefins and alcohols, the corresponding carboxylic acid product is valeric acid;
[0014] When the olefin and its alcohol are pentene and pentanol, the corresponding carboxylic acid product is 2,2-dimethylbutyric acid;
[0015] When the olefin and its alcohol are hexene and hexanol, the corresponding carboxylic acid product is heptanoic acid;
[0016] When the olefin and its alcohol are hepten and heptanol, the corresponding carboxylic acid product is octanoic acid;
[0017] When the olefin and its alcohol are octene and octanol, the corresponding carboxylic acid product is nonanoic acid.
[0018] Optionally, 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.
[0019] 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).
[0020] Optionally, the silicon-to-aluminum atomic ratio of the zeolite molecular sieve is 5 to 120.
[0021] 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.
[0022] 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.
[0023] Optionally, the zeolite molecular sieve is modified; the modification is metal element modification or silanization modification;
[0024] The metallic element is selected from at least one of Fe, Cu, Zn, Ga, and Ag;
[0025] The silane is selected from at least one of silanes, silicates, and silica sols.
[0026] Optionally, the solid acid catalyst is a shaped acidic zeolite molecular sieve;
[0027] It is obtained by mixing acidic zeolite molecular sieves and matrix, kneading, extruding into strips, drying, and calcining;
[0028] The matrix is selected from at least one of alumina, silicon dioxide, magnesium oxide, and kaolin.
[0029] The mass content of acidic zeolite molecular sieve is 50-100%.
[0030] 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.
[0031] 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.
[0032] Optionally, the molar ratio of CO to the olefin and its alcohol is 0.05:1 to 200:1.
[0033] Preferably, the molar ratio of CO to the olefin and its alcohol is 2:1 to 80:1.
[0034] Optionally, the molar ratio of CO to the olefin and its alcohol 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.
[0035] Optionally, the raw material further contains water, and the molar ratio of water to the olefin and its alcohol is 0:1 to 20:1.
[0036] Preferably, the molar ratio of water to the olefin and its alcohol is 1:1 to 10:1.
[0037] Optionally, the molar ratio of water to the olefin and its alcohol is independently selected from any value or a range between 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, and 20:1.
[0038] Optionally, the raw material gas contains other gases;
[0039] The other gases are selected from at least one of hydrogen, nitrogen, helium, argon, and carbon dioxide;
[0040] The other gases comprise 0 to 50% of the volume of CO gas.
[0041] 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.
[0042] Optionally, when the olefin and its alcohol are only butene or butanol, their normal-to-iso ratio is 0.2 to 16:1.
[0043] Optionally, when the olefin and its alcohol are only butene or butanol, their normal-to-iso ratio is 0.5 to 8:1.
[0044] Optionally, the reaction temperature is 50–300°C.
[0045] Preferably, the reaction temperature is 100-220°C.
[0046] Optionally, the temperature of the reaction is independently selected from any value of 50°C, 100°C, 150°C, 200°C, 250°C, 300°C, or a range between any two.
[0047] Optionally, the reaction pressure is 0.1 to 20 MPa.
[0048] Optionally, the reaction pressure is 0.1 to 15 MPa.
[0049] Preferably, the reaction pressure is 1.0 to 8.0 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 (WHSV) of the olefin and its alcohol is 0.001–20.0 h⁻¹. -1 .
[0052] Preferably, the mass hourly space velocity (MSV) of the olefin and its alcohol is 0.05–10.0 h⁻¹. -1 .
[0053] More preferably, the mass hourly space velocity (HHSV) of the olefin and its alcohol is 0.1–5.0 h⁻¹. -1 .
[0054] Optionally, the mass hourly space velocity (MSV) of the olefin and / or alcohol 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.
[0055] Optionally, the reaction is carried out in a reactor;
[0056] The reactor includes at least one of a fixed-bed reactor, a fluidized-bed reactor, and a moving-bed reactor.
[0057] Those skilled in the art can select a suitable reactor based on actual production needs. Preferably, the reactor is a fixed-bed reactor.
[0058] The beneficial effects that this application can produce include:
[0059] 1) The method for preparing carboxylic acids from olefins and their alcohols provided in this application can efficiently and stably obtain carboxylic acids, especially the product carboxylic acid, which has high selectivity. Correspondingly, the production and separation energy consumption is low. Therefore, this method has broad application prospects.
[0060] 2) The method for preparing carboxylic acids from olefins and alcohols 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
[0061] Figure 1 shows the XRD pattern of the hydrogen-type molecular sieve sample prepared in Example 1. Detailed Implementation
[0062] The present application is described in detail below with reference to the embodiments, but the present application is not limited to these embodiments.
[0063] Unless otherwise specified, the raw materials and catalysts used in the embodiments of this application were all purchased commercially.
[0064] Unless otherwise specified, all test methods are standard and all instrument settings are those recommended by the manufacturer.
[0065] 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 nomenclature of the molecular sieves are shown in Table 1. In Table 1:
[0066] 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.
[0067] The method for synthesizing 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.
[0068] The method for synthesizing BEA molecular sieves comes from the literature TAKEWAKI T, HWANG SJ, YAMASHITA H, et al. Synthesis of *BEA-type molecular sieves using mesoporous materials as reagents[J]. Microporous and Mesoporous Materials, 1999, 32(3):265-78.
[0069] The analysis method in the embodiments of this application is as follows:
[0070] The effluent after the reaction was analyzed online using an Agilent 7890B gas chromatograph. The FID detector was connected to an FFAP capillary column, and the TCD detector was connected to a Porapak Q packed column.
[0071] In the embodiments of this application, the conversion rate and selectivity are calculated as follows:
[0072] In the examples, the conversion rates of olefins and / or alcohols were calculated using the internal standard method, and the product selectivity was calculated using the normalization method.
[0073] Olefin and / or alcohol conversion rate = [(number of carbon moles of olefins and / or alcohols in the feed gas) - (number of carbon moles of olefins and / or alcohols in the product)] ÷ (number of carbon moles of olefins and / or alcohols in the feed gas) × (100%)
[0074] Product selectivity = (number of carbon moles in the product ÷ total number of carbon moles in the organic matter of the product) × 100%.
[0075] Table 1. Sources and silicon-to-aluminum ratios of different catalysts
[0076] Example 1 Catalyst Preparation
[0077] Preparation of acidic zeolite molecular sieves
[0078] The Na-type molecular sieves in Table 1 were obtained by ion exchange with NH4NO3 and drying and calcining.
[0079] 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.
[0080] 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.
[0081] 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. A graphite monochromator with Ni filter was used, with a tube voltage of 40 kV, a tube current of 40 mA, a scanning speed of 5° / min, and a scanning area of 5-60°. Figure 1 shows the XRD patterns of representative hydrogen-form molecular sieve samples prepared in Example 1, such as ZSM-5, ZSM-35, MCM-22, and ZSM-22. As can be seen from the figure, the prepared hydrogen-form samples all maintained typical characteristic peaks, indicating that the samples were not damaged during the preparation process.
[0082] Preparation of matrix-containing samples
[0083] The matrix-containing molded hydrogen form sample was prepared by extrusion molding.
[0084] 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.
[0085] 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#.
[0086] 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#.
[0087] 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#.
[0088] 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#.
[0089] Preparation of metal-modified samples
[0090] Metal-modified hydrogen-form samples were prepared by impregnation or ion exchange.
[0091] 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.
[0092] 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#.
[0093] 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#.
[0094] Preparation of metal-modified HZSM-35 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)-21-25#.
[0095] Preparation of silanized modified HZSM-35 molecular sieve: 10g of raw material sample HZSM-23 was mixed with 4g of pre-prepared silica sol containing 5wt% Si source, silane or silicate ester aqueous solution, and deionized water was added to adjust the solid-liquid ratio to 1:5; the solution was stirred for 2h under a water bath heating condition of ~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)-26#.
[0096] 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.
[0097] Table 2 Sample number and sample composition
[0098] Example 2: Preparation of valeric acid from butene using 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 (HHSV) of the butene feed was 0.4h. -1 The molar ratio of carbon monoxide to butene was 60:1; the molar ratio of water to butene was 1:1; the ratio of n-isobutene was 2:1; and the catalytic reaction was carried out for 8 hours at a reaction temperature of 200℃. The reaction results are shown in Table 3.
[0100] Table 3. Reaction results on different catalysts
[0101] As shown in Table 3, solid acid catalysts based on acidic zeolite molecular sieves can achieve the purpose of butene to valeric acid.
[0102] Example 3: Preparation of valeric acid from butene at different reaction temperatures
[0103] Catalyst H-1# was used as the sample, 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 4.
[0104] Table 4. Reaction results at different reaction temperatures.
[0105] As shown in Table 4, the reaction temperature has a significant impact on the preparation of pentanoic acid from butene. As the temperature increases, the butene conversion rate increases. However, when the reaction temperature exceeds 200℃, it promotes the formation of a large number of polymeric hydrocarbons, which leads to a decrease in the selectivity of pentanoic acid.
[0106] Example 4: Preparation of valeric acid from butene under different reaction pressures
[0107] Catalyst H-1# was used as the sample, 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 5.
[0108] Table 5. Reaction results under different reaction pressures.
[0109] Table 5 shows that increasing the reaction pressure helps promote the preparation of valeric acid from butene, and the reaction pressure is directly proportional to the butene conversion rate. At low pressure, the product significantly promotes the selectivity of pentanoic acid, while at high pressure, it significantly promotes the selectivity of other valeric acids.
[0110] Example 5: Preparation of valeric acid from butene at different mass space velocities
[0111] Using catalyst H-1# as the sample, the mass hourly space velocities (HHSVs) of 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 6.
[0112] Table 6. Reaction results at different butene mass space velocities.
[0113] As shown in Table 6, the higher the reaction space velocity, the lower the butene conversion rate, while the selectivity of valeric acid is basically unaffected.
[0114] Example 6: Preparation of valeric acid from butene under different carbon monoxide and butene molar ratios
[0115] Using catalyst H-1# as the sample, the molar ratios of CO and 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 8 hours are shown in Table 7.
[0116] Table 7. Reaction results with different molar ratios of carbon monoxide and butene.
[0117] As shown in Table 7, the ratio of carbon monoxide to butene has a significant impact on butene conversion; the higher the ratio, the higher the selectivity of valeric acid.
[0118] Example 7: Preparation of valeric acid from butene under different water and butene molar ratios
[0119] Using catalyst H-1# as the sample, the molar ratios of water and 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 8 hours are shown in Table 8.
[0120] Table 8. Reaction results with different water and butene molar ratios.
[0121] As shown in Table 8, the proportion of water has a significant impact on butene conversion. An appropriate proportion is beneficial to improving catalyst activity; however, if the proportion is too high, the catalyst activity will be significantly reduced.
[0122] Example 8: Preparation of valeric acid from butene under different molar ratios of n- and isobutene
[0123] Using catalyst H-1# as the sample, the molar ratios of butene (normal and different) were 0, 0.5, 1, 2, 4 and 8, respectively. Other conditions were the same as in Example 2. The results of the reaction running for 8 hours are shown in Table 9.
[0124] Table 9. Reaction results for different butene-to-isor ratios.
[0125] As shown in Table 9, the ratio of n-butene to isobutene has a significant impact on the reactivity. It is worth noting that when there is no n-butene in the raw material, the conversion rate of isobutene and the selectivity of tervastatin are both greater than 90%, indicating extremely high reactivity.
[0126] Example 9: Preparation of valeric acid from butene when the carbon monoxide feed gas contains any one or more of hydrogen, nitrogen, helium, argon, carbon dioxide, etc.
[0127] Catalyst H-1# was used as the sample. Other gases contained in CO are shown in Table 10. Other conditions were the same as in Example 2. The reaction was run for 8 hours and the results are shown in Table 10.
[0128] Table 10. Reaction results when carbon monoxide feed gas contains other gases.
[0129] Table 10 shows that the increase of impurity gases in carbon monoxide directly leads to a decrease in the ratio of carbon monoxide to butene, and a reduction in the selectivity of valeric acid. The presence of hydrogen gas also leads to a decrease in catalyst activity.
[0130] Example 10: Direct conversion of pentene to 2,2-dimethylbutyric acid using different catalysts
[0131] 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 (HHSV) of the pentene feed was 0.4h. -1 The molar ratio of carbon monoxide to pentene was 90:1; the molar ratio of water to pentene 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 11.
[0132] Table 11 Reaction results on different catalysts
[0133] As shown in Table 11, solid acid catalysts based on acidic zeolite molecular sieves can achieve the purpose of producing 2,2-dimethylbutyric acid from pentene.
[0134] Example 11: Preparation of 2,2-dimethylbutyric acid from pentene at different reaction temperatures
[0135] Catalyst H-29# was used as the sample, and the reaction temperatures ranged from 100 to 250°C. Other reaction conditions were the same as in Example 10. The results of the catalytic reaction after 8 hours are shown in Table 12.
[0136] Table 12 Reaction results at different reaction temperatures
[0137] As shown in Table 12, temperature has a significant impact on the preparation of 2,2-dimethylbutyric acid from pentene. As the temperature increases, the conversion rate of pentene increases. However, excessively high temperatures will promote the formation of a large number of polymeric hydrocarbons, thereby reducing the overall selectivity of 2,2-dimethylbutyric acid.
[0138] Example 12: Preparation of 2,2-dimethylbutyric acid from pentene under different reaction pressures
[0139] Catalyst H-29# was used as the sample, and the reaction pressures were 0.1 MPa, 5 MPa, 10 MPa and 15 MPa, respectively. Other conditions were the same as in Example 10. The reaction ran for 8 hours and the results are shown in Table 13.
[0140] Table 13 Reaction results under different reaction pressures
[0141] As shown in Table 13, increasing the reaction pressure helps to promote the preparation of 2,2-dimethylbutyric acid from pentene, and the reaction pressure is directly proportional to the conversion rate of pentene; after the pressure increases to a certain extent, the product selectivity does not change significantly.
[0142] Example 13: Preparation of 2,2-dimethylbutyric acid from pentene at different pentene mass space velocities
[0143] Using catalyst H-29# as the sample, the mass hourly space velocities (HHSVs) of pentene were 0.02, 0.4, 1, and 4 h⁻¹. -1 Other conditions were the same as in Example 10, and the results after 8 hours of reaction are shown in Table 14.
[0144] Table 14 Reaction results at different pentene mass space velocities
[0145] As shown in Table 14, the higher the catalyst loading, the lower the pentene conversion rate, while the selectivity of 2,2-dimethylbutyric acid remains largely unaffected.
[0146] Example 14: Direct conversion of pentene to prepare 2,2-dimethylbutyric acid under different carbon monoxide and pentene molar ratios.
[0147] Using catalyst H-29# as the sample, the molar ratios of CO and pentene were 0.05, 1, 6, 40, 80 and 90, respectively. Other conditions were the same as in Example 10. The results of the reaction running for 8 hours are shown in Table 15.
[0148] Table 15 Reaction results with different molar ratios of carbon monoxide and pentene
[0149] As shown in Table 15, the ratio of carbon monoxide to pentene has a significant impact on the conversion of pentene; the higher the ratio, the higher the selectivity of 2,2-dimethylbutyric acid.
[0150] Example 15: Direct conversion of pentene to prepare 2,2-dimethylbutyric acid under different water-to-pentene molar ratios.
[0151] Using catalyst H-29# as the sample, the molar ratios of water and pentene were 0.5, 1, 2, 4, 16 and 32, respectively. Other conditions were the same as in Example 10. The results of the reaction running for 8 hours are shown in Table 16.
[0152] Table 16 Reaction results with different molar ratios of water and pentene
[0153] As shown in Table 16, the ratio of water to pentene has a significant impact on pentene conversion. An appropriate ratio is beneficial to improving catalyst activity; however, if the ratio is too high, the molecular sieve activity will be significantly reduced.
[0154] Example 16: 2,2-Dimethylbutyric acid is prepared by direct conversion of pentene when the carbon monoxide feed gas contains any one or more of hydrogen, nitrogen, helium, argon, carbon dioxide, etc.
[0155] Catalyst H-29# was used as the sample. Other gases contained in CO are shown in Table 25. Other conditions were the same as in Example 10. The results of the reaction running for 8 hours are shown in Table 17.
[0156] Table 17 Reaction results when carbon monoxide feed gas contains other gases
[0157] Table 17 shows that the increase of impurity gases in carbon monoxide directly leads to a decrease in the ratio of carbon monoxide to pentene, and a decrease in the selectivity of 2,2-dimethylbutyric acid. The presence of hydrogen gas causes a sharp decrease in catalyst activity.
[0158] Example 17 Results of the reaction of different olefins on a molecular sieve catalyst
[0159] 1g of the molecular sieve catalyst 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 (MSV) of the olefins (hexene, hepten, or octene, respectively) was 0.4h. -1 The molar ratio of carbon monoxide to olefins was 60:1; the molar ratio of water to olefins 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 Tables 18, 19, and 20.
[0160] Table 18 shows the reaction results of hexene on different molecular sieve catalysts.
[0161] Table 1. Reaction results of 19-heptene on different molecular sieve catalysts
[0162] Table 20 Results of octene reaction on different molecular sieve catalysts
[0163] As shown in Tables 18, 19 and 20, acidic zeolite molecular sieves can be used as catalysts to achieve the conversion of hexene, heptene and octene into heptanoic acid, octanoic acid and nonanoic acid, respectively.
[0164] Example 18: Results of the reaction of butanol on a molecular sieve catalyst
[0165] 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 butanol feed was 0.6h⁻¹. -1 The molar ratio of carbon monoxide to butanol was 60:1; the molar ratio of water to butanol was 0:1; the ratio of n-isobutanol was 2:1; and the catalytic reaction was carried out for 8 hours at a reaction temperature of 200℃. The reaction results are shown in Table 21.
[0166] Table 21 Results of butanol reaction on different molecular sieve catalysts
[0167] As shown in Table 21, acidic zeolite molecular sieves can be used as catalysts to achieve the conversion of butanol into valeric acid.
[0168] Example 19 Results of the reaction of hexanol / octanol on a molecular sieve catalyst
[0169] 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 hexanol feed was 0.6h⁻¹. -1 The molar ratio of carbon monoxide to hexanol was 60:1; the molar ratio of water to hexanol was 0:1; the catalytic reaction was carried out for 8 hours at a reaction temperature of 200℃, and the reaction results are shown in Tables 22 and 23.
[0170] Table 22 Results of hexanol reaction on different molecular sieve catalysts
[0171] Table 23 Results of octanol reaction on different molecular sieve catalysts
[0172] As shown in Tables 22 and 23, acidic zeolite molecular sieves can be used as catalysts to achieve the conversion of hexanol and octanol into heptanoic acid and nonanoic acid.
[0173] Example 20: Results of the preparation of carboxylic acids from different olefins and corresponding alcohols in different reactors
[0174] 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 24.
[0175] Table 24 Reaction results in different reactors
[0176] Using catalyst H-29# as the sample, fixed bed, fluidized bed and moving bed were used respectively, with other conditions the same as in Example 10. The reaction was run for 8 hours, and the results are shown in Table 25.
[0177] Table 25 Reaction results in different reactors
[0178] The catalyst used was sample H-29, and the reaction was carried out in fixed bed, fluidized bed and moving bed, respectively. Other conditions were the same as in Example 17. The reaction was run for 8 hours, and the results are shown in Table 26.
[0179] Table 26 Reaction results in different reactors
[0180] 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 17. The reaction was run for 8 hours, and the results are shown in Table 27.
[0181] Table 27 Reaction results in different reactors
[0182] The catalyst used was sample H-29#, and the reaction was carried out in fixed bed, fluidized bed and moving bed, respectively. Other conditions were the same as in Example 17. The reaction was run for 8 hours, and the results are shown in Table 28.
[0183] Table 28 Reaction results in different reactors
[0184] 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 18. The reaction was run for 8 hours, and the results are shown in Table 29.
[0185] Table 29 Reaction results in different reactors
[0186] 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 19. The reaction was run for 8 hours, and the results are shown in Tables 30 and 31.
[0187] Table 30 Reaction results in different reactors
[0188] Table 31 Reaction results in different reactors
[0189] As shown in Tables 24-31, different reactor types can all achieve the conversion of multicarbon olefins and corresponding alcohols into carboxylic acids.
[0190] Example 21 Results of preparing carboxylic acids from different olefins and corresponding alcohols after regeneration of deactivated catalysts in different olefin and alcohol systems
[0191] Specifically, several deactivated catalysts for different olefin or alcohol systems were regenerated at 550°C for 12 hours in air. After regeneration, 1 g of the regenerated catalyst (H-1#-re, H-29#-re) for each system 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 maintained for 4 hours. Then, the temperature was lowered to 200°C 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 (MSV) of the olefins (hexene, hepten, or octene, respectively) was 0.4 h⁻¹. -1 The molar ratio of carbon monoxide to olefins was 60:1; the molar ratio of water to olefins was 1:1; and the catalytic reaction was carried out for 8 hours at a reaction temperature of 200°C. Additionally, the mass hourly space velocity (HHSV) of the corresponding alcohol feed was 0.6 h⁻¹. -1 The molar ratio of carbon monoxide to the corresponding alcohol was 60:1; the molar ratio of water to hexanol was 0:1; and the catalytic reaction was carried out for 8 hours at a reaction temperature of 200℃. The reaction results are shown in Table 32.
[0192] Table 32 Results of catalytic conversion of olefins to carboxylic acids using the corresponding regenerated catalysts
[0193] As shown in Table 32, the reactivity of the deactivated catalyst after regeneration is basically the same as that of the fresh catalyst.
[0194] 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 all fall within the scope of the technical solution.
Claims
A method for preparing carboxylic acids from olefins and their alcohols, characterized in that, The method includes: A feed gas containing olefins and their alcohols, CO, and a solid acid catalyst is contacted and reacted to yield carboxylic acids. The olefins and their alcohols are selected from at least one of C4-C8 olefins and C4-C8 alcohols; The solid acid catalyst includes zeolite molecular sieves. The method according to claim 1, characterized in that, C4 olefins are selected from at least one of 1-butene, 2-butene, and isobutene; C4 alcohols are selected from at least one of n-butanol, isobutanol, and tert-butanol. C4 + The olefin is selected from at least one of pentene, hexene, hepten, and octene; C4 + The alcohol is selected from at least one of pentanol, hexanol, heptanol, and octanol. The method according to claim 1 or 2, characterized in that, When the olefin and its alcohol are C4 olefins and alcohols, the corresponding carboxylic acid product is valeric acid; When the olefin and its alcohol are pentene and pentanol, the corresponding carboxylic acid product is 2,2-dimethylbutyric acid; When the olefin and its alcohol are hexene and hexanol, the corresponding carboxylic acid product is heptanoic acid; When the olefin and its alcohol are hepten and heptanol, the corresponding carboxylic acid product is octanoic acid; When the olefin and its alcohol are octene and octanol, the corresponding carboxylic acid product is nonanoic acid. The method according to any one of claims 1 to 3, characterized in that, 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. The method according to any one of claims 1 to 4, 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. The method according to any one of claims 1 to 5, characterized in that, The silicon-to-aluminum atomic ratio of the zeolite molecular sieve is 5 to 120. The method according to any one of claims 1 to 6, 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. The method according to any one of claims 1 to 7, 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%. The method according to any one of claims 1 to 8, characterized in that, The molar ratio of CO to the olefin and its alcohol is 0.05:1 to 200:
1. The method according to any one of claims 1 to 9, characterized in that, The molar ratio of CO to its alcohol is 2:1 to 80:
1. The method according to any one of claims 1 to 10, characterized in that, The raw gas also contains water, and the molar ratio of water to the olefin and its alcohol is 0:1 to 20:
1. The method according to any one of claims 1 to 11, characterized in that, The raw gas also contains water, and the molar ratio of water to the olefin and its alcohol is 1:1 to 10:
1. The method according to any one of claims 1 to 12, characterized in that, The raw material gas contains other gases; The other gases are selected from at least one of hydrogen, nitrogen, helium, argon, and carbon dioxide; The other gases account for 0 to 50% of the volume of CO gas. The method according to any one of claims 1 to 13, characterized in that, The reaction temperature is 50–300°C. The method according to any one of claims 1 to 14, characterized in that, The reaction temperature is 100-220℃. The method according to any one of claims 1 to 15, characterized in that, The reaction pressure is 0.1–20 MPa. The method according to any one of claims 1 to 16, characterized in that The reaction pressure is 1.0 to 15.0 MPa. The method according to any one of claims 1 to 17, characterized in that, The mass hourly space velocity (MSV) of the olefins and their alcohols is 0.001–20.0 h⁻¹. -1 . The method according to any one of claims 1 to 18, characterized in that, The mass hourly space velocity (MSV) of the olefins and their alcohols is 0.05–10.0 h⁻¹. -1 . The method according to any one of claims 1 to 19, characterized in that, The mass hourly space velocity (MSV) of the olefins and their alcohols is 0.1–5.0 h⁻¹. -1 . The method according to any one of claims 1 to 20, characterized in that, The reaction is carried out in a reactor; The reactor includes at least one of a fixed-bed reactor, a fluidized-bed reactor, and a moving-bed reactor.