CN113877583A - Catalyst in process for producing 1, 5-pentanediol by biological furfuryl alcohol hydrogen ring-opening, preparation and application - Google Patents
Catalyst in process for producing 1, 5-pentanediol by biological furfuryl alcohol hydrogen ring-opening, preparation and application Download PDFInfo
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Abstract
The invention relates to the field of catalysis, and discloses a catalyst in a process for producing 1, 5-pentanediol by biological furfuryl alcohol hydrogen ring-opening, and preparation and application thereof. The catalyst is MOx-M/protonic acid catalyst or MOx-M '/protonic acid catalyst, wherein the component MOx is one metal oxide of Co, Ni, Cu and W, and M or M' is Co, Ni, Cu,One metal of W; the carrier used by the catalyst is mainly SiO2/Al2O3MFI structure molecular sieve and FAU structure molecular sieve with the mol ratio of 18-130; the MOx loading in the catalyst is 0-25%, and the M or M' loading is 0-25%; when the catalyst is applied to a fixed bed reactor, the reaction temperature is 100-200 ℃, and the hydrogen pressure is 1-6 MPa. The method does not use expensive noble metal catalyst and rare petroleum-based raw materials, has the characteristics of low preparation cost, mild reaction conditions, high raw material conversion rate and high yield of the 1, 5-pentanediol, and has obvious economic benefit and environmental benefit.
Description
Technical Field
The invention relates to the field of catalysis, and in particular relates to a catalyst in a process for producing 1, 5-pentanediol by biological furfuryl alcohol hydrogen ring-opening, and preparation and application thereof.
Background
1, 5-pentanediol is widely applied to fine chemical engineering as an important dihydric alcohol, not only is a monomer for producing unsaturated polyester and polyurethane, but also is used in the fields of food, medicine, cosmetics and the like, and is also used as a raw material of a solvent or a wetting agent of a surfactant, a special detergent, high-end ink, emulsion paint and the like.
1, 5-pentanediol is used as an important polymerization monomer, the global yield is only 3000 tons/year at present, and the price is 6000 dollars/ton; because of the shortage of 1, 5-pentanediol raw material, high price and the like, the yield of the polymerization product with special thermodynamic property is low, and only BASF and UBE are applied to a few fields at present.
The raw material of the 1, 5-pentanediol is mainly derived from glutaric acid and derivatives thereof, is produced by adopting a hydrofining process, and is a main way for producing the 1, 5-pentanediol at present.
Chinese patent CN1565728A describes that glutaric acid is used as a raw material to prepare 1, 5-methyl glutarate through esterification reaction, and then 1, 5-pentanediol is prepared through hydrogenation at 150-350 ℃ and 3-5MPa under the action of a copper-zinc-aluminum catalyst; however, the process flow is relatively long, and glutaric acid is derived from petroleum-based raw materials, with limited yields, resulting in relatively high costs.
Chinese patent CN101270032B describes that 1, 5-glutaraldehyde is used as a raw material, a supported catalyst with Ru as an active component is adopted, the reaction temperature is 60-120 ℃, the reaction pressure is 2-8MPa, and 1, 5-pentanediol is prepared by hydrogenation; the defects of the technology are that the source of the used raw materials is limited, and the cost of the catalyst is high.
Furfuryl alcohol and tetrahydrofurfuryl alcohol are important substances of a biomass conversion chemical platform structure, have the advantages of reproducibility, wide sources and low cost, and can obtain the 1, 5-pentanediol with high added value by hydrogenation first and then ring opening or hydrogenation first and then ring opening. The biomass-based raw material is expected to improve the problems of lack of petroleum-based C5 source, large carbon emission and the like, and is in accordance with the development trend of 'carbon neutralization and green sustainable'.
The Chinese patent CN103848719A uses a biomass-based raw material tetrahydrofurfuryl alcohol, adopts an A-B/carrier type catalyst loaded with noble metals Rh and Ir to prepare 1, 5-pentanediol under the reaction pressure of 6MPa, and widens the raw material source, but the method has higher reaction pressure, the product yield is only 55.4 percent, and the cost of the adopted catalyst is high.
Tomishige et al, Japan, uses M-M' Ox/SiO2M-M 'Ox/C type catalyst (Shuichi Koso, Naoyuki Ueda, Yasunori Shinmi, Kazu Okumura, Tokushi Kizuka, Keiichi Tomishige. journal of Catalysis 267 (2009) 89-92), wherein M is an expensive Rh catalyst, M' is Re, Mo, W metal, and the carrier is SiO free of acidity2And C, taking tetrahydrofurfuryl alcohol as a raw material, reacting for 4 hours at 120 ℃ under 8MPa by following a hydrogenolysis ring opening mechanism to obtain 50.1 percent of tetrahydrofurfuryl alcohol conversion rate and 95.5 percent of 1, 5-pentanediol selectivity, and the yield is the highest reported yield at present. However, hydrogenolysis ring opening requires a relatively high reaction pressure and a noble metal Rh with high hydrogenolysis activity.
Furfuryl alcohol serving as a furfural derivative is industrially produced on a large scale, and has rich electron furan rings, so that various chemical reactions can be carried out, and compared with a hydrogenolysis ring-opening idea of tetrahydrofurfuryl alcohol, the method is easier to realize, milder in conversion conditions and free of noble metals with high hydrogenolysis activity based on an acidic ring-opening idea; however, too many reaction paths and a higher proportion of by-products in the product are still challenging for the preparation of 1, 5-pentanediol with high selectivity. The method develops a high-efficiency, high-yield, green and low-cost catalytic system, realizes the conversion of the furfuryl alcohol to the 1, 5-pentanediol, can get rid of the dependence on petroleum resources to a certain extent, and has important significance for reducing the production cost and realizing carbon neutralization.
The research institute of chemistry and physics of Lanzhou, the Chinese academy, found that the calcium titanium is adoptedMineral structure derived Cu-LaCoO3The catalyst has good effect on furfuryl alcohol conversion (Fangfang Gao, Hailong Liu, Xun Hu, jin Chen, Zhiwei Huang, Chungu Xia, Chinese Journal of Catalysis 39(2018)1711-1723), and the selectivity of 1, 5-pentanediol can reach 40% at 140 ℃ and 6MPa in a batch reactor, and the yield is 40.3%.
Taylor P et Al in the United states used a mixed oxide of non-noble metals Cu-Co-Al (Taylor P, Sulmonetti, Bo Hu, Sungsik Lee, Pradeep K. agrawal, and Christopher W. Jones, ACS Sustainable Chem. Eng.2017,5, 8959-8969) with furfuryl alcohol as the starting material achieved 42% selectivity in a batch reactor, which is the highest selectivity reported at present.
In conclusion, due to the complex product types, the selectivity of the catalytic reaction is poor by adopting the existing process and the catalyst thereof, the yield of the 1, 5-pentanediol is low, the technical economy is not high, and the large-scale application in the industry is limited. Therefore, a catalyst with high activity, high selectivity and low cost is needed to realize the preparation of 1, 5-pentanediol from biomass-based furfuryl alcohol.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a catalyst in a process for producing 1, 5-pentanediol by the hydrogen ring opening of biological furfuryl alcohol, and preparation and application thereof, and the technical scheme is as follows:
a catalyst in a process of producing 1, 5-pentanediol by the hydrogen ring opening of biological furfuryl alcohol adopts a supported catalyst, and is characterized in that the catalyst is an MOx-M/protonic acid catalyst or an MOx-M'/protonic acid catalyst; wherein, the component MOx is one metal oxide of Co, Ni, Cu and W, and M or M' is one metal of Co, Ni, Cu and W.
The carrier adopted by the catalyst is MFI structure molecular sieve, FAU structure molecular sieve, TS-1 molecular sieve and Al2O3Carrier, SiO2One kind of carrier.
SiO in the MFI structure molecular sieve and FAU structure molecular sieve2/Al2O3The molar ratio is 18-130.
SiO in the TS-1 molecular sieve2/TiO2The molar ratio is 40-100.
The loading of MOx in the catalyst is 0-25%, and the loading of M or M' is 0-25%.
The sum of the loading amounts of MOx and M or M' in the catalyst is 5-15%.
The catalyst is prepared by adopting an impregnation method; the impregnation method comprises an excess impregnation method, an equal-volume impregnation method and a plurality of step-by-step impregnation methods.
A preparation method of a catalyst in a process of producing 1, 5-pentanediol by the hydrogen ring opening of biological furfuryl alcohol comprises the following preparation steps:
preparation of MOx-M/protonic acid catalyst: dissolving soluble salt of M in deionized water to prepare solution with a certain concentration, adding a powder type carrier according to a metering ratio for impregnation, standing and aging for 6-10h, drying at 100 ℃ for 12h, roasting at 500-600 ℃ for 3-6 h, and tabletting for molding;
preparation of MOx-M'/protonic acid catalyst: respectively preparing soluble salt solutions of M and M' with certain concentrations, uniformly mixing according to a metering ratio, soaking on carrier powder, standing and aging for 6-10h, drying at 100 ℃ for 12h, roasting at 500-600 ℃ for 3-6 h, and tabletting for molding.
An application method of a catalyst in a process of producing 1, 5-pentanediol by the hydrogen ring opening of biological furfuryl alcohol, wherein the catalyst is applied to a high-pressure reaction kettle or a fixed bed reactor; the activation conditions of the catalyst before use were: the partial pressure of the reduced hydrogen is 0.1-4MPa, the reduction temperature is 200-450 ℃, and the reduction time is 2-6 hours; the reaction conditions of the catalyst applied to the fixed bed reactor are as follows: ethanol is used as a solvent, the mass concentration of the furfuryl alcohol solution is 2-100%, the reaction temperature is 100-200 ℃, and the hydrogen pressure is 1-6 MPa.
The partial pressure of reducing hydrogen under the activation condition is 1-3MPa, the reduction temperature is 250-350 ℃, and the reduction time is 3-5 hours; the reaction temperature of the reaction conditions is 120-160 ℃, and the hydrogen pressure is 2-4 MPa.
Compared with the prior art, the invention mainly has the following beneficial technical effects:
1. the invention does not use expensive noble metal catalyst and rare petroleum-based raw material, takes furfuryl alcohol obtained from biomass such as corncob and bagasse as raw material, is a new way for preparing 1, 5-pentanediol with high added value, embodies low cost, good sustainability and environmental protection, and has obvious economic benefit and environmental benefit.
2. The invention adopts an acidic ring-opening and post-hydrogenation mechanism, and constructs a high-efficiency bifunctional catalyst by utilizing the functional characteristics of valence controllability and hydrogen dissociation of Cu metal in the reaction based on the unique framework structure, catalytic performance, adjustable pore size and acidic property of MFI and FAU molecular sieves.
3. The invention can make the conversion rate of furfuryl alcohol reach more than 98% and the selectivity of 1, 5-pentanediol reach more than 80% under mild reaction conditions.
Drawings
FIG. 1 is a graph of the effect of different reactive metals on the reaction;
FIG. 2 is a graph showing the effect of different supports on the selectivity of furfuryl alcohol hydrogenolysis ring opening to 1, 5-pentanediol;
FIG. 3 shows the effect of different Si/Al ratios on the selectivity of furfuryl alcohol for ring-opening to produce 1, 5-pentanediol;
FIG. 4 is a graph showing the effect of different metal contents on the selectivity of furfuryl alcohol ring opening to 1, 5-pentanediol.
Detailed Description
The present invention will be described in detail below with reference to the following examples and accompanying drawings.
Example 1
Preparation of MO by impregnation methodx-M'/protonic acid catalyst
Cu (NO) was prepared at a concentration of 20wt%, respectively3)2·3H2O and Co (NO)3)2·6H2O solution; and (3) mixing the solution according to the molar ratio of Cu to Co of 1: 1, uniformly mixing; soaking the mixture on alumina powder according to the mixed metal loading of 10% by weight by an isometric soaking method, standing and aging for 6h, drying at 100 ℃ for 12h, roasting in a muffle furnace at 500 ℃ for 3h to obtain a supported catalyst, and performing hydrogen pretreatment to obtain Cu-CoOx/Al2O3A catalyst of the type (I) is provided.
Example 2
Preparation of MO by impregnation methodx-M'/protonic acid catalyst
Cu (NO) was prepared at a concentration of 20wt%, respectively3)2·3H2O and Co (NO)3)2·6H2O solution; and (3) mixing the solution according to the molar ratio of Cu to Co of 1: 1, uniformly mixing; soaking the mixture on alumina powder according to the mixed metal loading of 10% wt by an isometric soaking method, standing and aging for 10h, drying at 100 ℃ for 12h, roasting in a muffle furnace at 600 ℃ for 6h to obtain a supported catalyst, and performing hydrogen pretreatment to obtain Cu-CoOx/Al2O3A catalyst of the type (I) is provided.
Examples 3 to 18
Preparation of MO by impregnation methodxM/Bronsted acid catalyst (M is Cu)
First Cu (NO)3)2·3H2Dissolving O in deionized water to prepare a solution with the concentration of 20%; adding different types of powder carriers according to the metering ratio for impregnation, standing and aging for 6-10h, drying at 100 ℃ for 12h, roasting at 500-600 ℃ for 3-6 h, and obtaining MO through hydrogen pretreatmentx-M/protonic acid catalyst.
Preparation of MO by impregnation methodxM/Bronsted acid catalyst (M is Ni)
Firstly, Ni (NO)3)2·3H2Dissolving O in deionized water to prepare a solution with the concentration of 20%; adding different types of powder carriers according to the metering ratio for impregnation, standing and aging for 6-10h, drying at 100 ℃ for 12h, roasting at 500-600 ℃ for 3-6 h, and obtaining MO through hydrogen pretreatmentx-M/protonic acid catalyst.
Preparation of MO by impregnation methodxM/Bronsted acid catalyst (M is Co)
First Co (NO)3)2·3H2Dissolving O in deionized water to prepare a solution with the concentration of 20%; adding different types of powder carriers according to the metering ratio for impregnation, standing and aging for 6-10h, drying at 100 ℃ for 12h, roasting at 500-600 ℃ for 3-6 h, and obtaining MO through hydrogen pretreatmentx-M/protonic acid catalyst.
Preparation of MO by impregnation methodxM/Bronsted acid catalyst (M is W)
Firstly (NH)4)6H2W12O40Dissolving in deionized water to prepare a solution with the concentration of 20%; adding different types of powder carriers according to the metering ratio for impregnation, standing and aging for 6-10h, drying at 100 ℃ for 12h, roasting at 500-600 ℃ for 3-6 h, and obtaining MO through hydrogen pretreatmentx-M/protonic acid catalyst.
The catalyst compositions of examples 3-18 are shown in Table 1.
TABLE 1
Note: MFI and FAU in Table 1 indicate that the molecular sieve structure is MFI type FAU type, and the numbers in parentheses after the MFI and FAU indicate SiO2/Al2O3A molar ratio; TS-1 indicates that the molecular sieve structure is TS-1 type, and the number in parentheses after the molecular sieve structure indicates SiO2/TiO2The molar ratio.
Example 19
Use of catalysts
When the catalyst is used in a continuous fixed bed, catalyst tablets in examples 1-18 are adopted, 2g of 20-40 mesh catalyst is selected and filled into a fixed bed reactor with the inner diameter of 8mm and the length of 30 cm; hydrogen pretreatment is carried out in a reactor, the pretreatment temperature is 300 ℃, the pressure is 1MPa, and the hydrogen flow rate is 40ml/min, and the pretreatment is carried out for 3 hours under the conditions; then, naturally cooling to the reaction temperature of 160 ℃, and adjusting the reaction pressure to 2.5 MPa; starting a feeding pump, wherein the feeding flow of the furfuryl alcohol solution is 0.4ml/min, the concentration of the furfuryl alcohol is 4% wt, starting sampling after the reaction is stable, and analyzing a sample by adopting gas chromatography.
Example 20
Use of catalysts
When the catalyst is used in a continuous fixed bed, catalyst tablets in examples 1-18 are adopted, 2g of 20-40 mesh catalyst is selected and filled into a fixed bed reactor with the inner diameter of 8mm and the length of 30 cm; hydrogen pretreatment is carried out in a reactor, the pretreatment temperature is 200 ℃, the pressure is 0.1MPa, the hydrogen flow rate is 40ml/min, and the pretreatment is carried out for 2 hours under the condition; then, naturally cooling to the reaction temperature of 100 ℃, and adjusting the reaction pressure to 1 MPa; starting a feeding pump, wherein the feeding flow of the furfuryl alcohol solution is 0.4ml/min, the concentration of the furfuryl alcohol is 2% wt, starting sampling after the reaction is stable, and analyzing a sample by adopting gas chromatography.
Example 21
Use of catalysts
When the catalyst is used in a continuous fixed bed, catalyst tablets in examples 1-18 are adopted, 2g of 20-40 mesh catalyst is selected and filled into a fixed bed reactor with the inner diameter of 8mm and the length of 30 cm; hydrogen pretreatment is carried out in a reactor, the pretreatment temperature is 450 ℃, the pressure is 4MPa, the hydrogen flow rate is 40ml/min, and the pretreatment is carried out for 6h under the condition; then, naturally cooling to the reaction temperature of 200 ℃, and adjusting the reaction pressure to 6 MPa; starting a feeding pump, wherein the feeding flow of the furfuryl alcohol solution is 0.4ml/min, the concentration of the furfuryl alcohol is 30% wt, starting sampling after the reaction is stable, and analyzing a sample by adopting gas chromatography.
Example 22
Use of catalysts
When the catalyst is used in a continuous fixed bed, catalyst tablets in examples 1-18 are adopted, 2g of 20-40 mesh catalyst is selected and filled into a fixed bed reactor with the inner diameter of 8mm and the length of 30 cm; hydrogen pretreatment is carried out in a reactor, the pretreatment temperature is 250 ℃, the pressure is 2MPa, the hydrogen flow rate is 40ml/min, and the pretreatment is carried out for 4 hours under the condition; then, naturally cooling to the reaction temperature of 120 ℃, and adjusting the reaction pressure to 2 MPa; starting a feeding pump, wherein the feeding flow of the furfuryl alcohol solution is 0.4ml/min, the concentration of the furfuryl alcohol is 4% wt, starting sampling after the reaction is stable, and analyzing a sample by adopting gas chromatography.
Example 23
Use of catalysts
When the catalyst is used in a continuous fixed bed, catalyst tablets in examples 1-18 are adopted, 2g of 20-40 mesh catalyst is selected and filled into a fixed bed reactor with the inner diameter of 8mm and the length of 30 cm; hydrogen pretreatment is carried out in a reactor, the pretreatment temperature is 350 ℃, the pressure is 3MPa, and the hydrogen flow rate is 40ml/min, and the pretreatment is carried out for 5 hours under the conditions; then, naturally cooling to the reaction temperature of 180 ℃, and adjusting the reaction pressure to 4 MPa; starting a feeding pump, wherein the feeding flow of the furfuryl alcohol solution is 0.4ml/min, the concentration of the furfuryl alcohol is 100% wt, sampling is started after the reaction is stable, and a sample is analyzed by gas chromatography.
The following brief analysis is carried out on the influence of different active metals on the reaction and the influence of different carriers, different silicon-aluminum ratios and different metal contents on the selectivity of the ring opening preparation of the 1, 5-pentanediol by the furfuryl alcohol by the attached drawings:
FIG. 1 is a graph that examines the effect of different reactive metals on the reaction and shows that: by comparing the reaction performance of the examples 4, 16, 17 and 18, the effect of the active metals Ni, Co, Cu and W on the ring opening of furfuryl alcohol is considered, the effect of the metal Cu is the best, and the selectivity of the 1, 5-pentanediol can reach more than 80%.
FIG. 2 is a graph which shows the selective effect of different carriers on the hydrogenolysis ring opening of furfuryl alcohol to produce 1, 5-pentanediol, as shown in the figure: al (Al)2O3And SiO2The carrier has unstable surface acidity and weak strength, so that the selectivity of 1, 5-pentanediol is low; TS-1 can obviously improve the selectivity of 1, 5-pentanediol, the FAU carrier shows the highest selectivity, and the selectivity is reduced quickly due to the poor structural stability of the FAU molecular sieve; MFI exhibits the best stability, the stability in industrial production is an important aspect for determining economic benefit, and the MFI carrier is comprehensively used to have the best effect.
FIG. 3 is a graph that examines the effect of different Si/Al ratios on the selectivity of furfuryl alcohol ring opening to produce 1, 5-pentanediol and is seen in the graph: the selectivity of 1, 5-pentanediol increases with decreasing silica-alumina ratio, and reaches the highest selectivity at a silica-alumina ratio of 40.
FIG. 4 is a graph showing the effect of different metal contents on the selectivity of furfuryl alcohol ring opening to 1, 5-pentanediol, as seen in the figure: the initial activity of the catalyst is not greatly different with the increase of the active metal component, but the selectivity of the 1, 5-pentanediol is obviously influenced by the metal loading on the catalyst with the increase of the reaction time, particularly the selectivity is obviously reduced after the metal content exceeds 20 percent, and the metal activity shows better selectivity within the range of 5 to 15 percent in the invention.
Claims (10)
1. A catalyst in a process of producing 1, 5-pentanediol by the hydrogen ring opening of biological furfuryl alcohol adopts a supported catalyst, and is characterized in that the catalyst is an MOx-M/protonic acid catalyst or an MOx-M'/protonic acid catalyst; wherein, the component MOx is one metal oxide of Co, Ni, Cu and W, and M or M' is one metal of Co, Ni, Cu and W.
2. The catalyst in the process for producing 1, 5-pentanediol through the hydroring opening of biological furfuryl alcohol according to claim 1, wherein the carrier used by the catalyst is MFI structure molecular sieve, FAU structure molecular sieve, TS-1 molecular sieve, Al2O3Carrier, SiO2One kind of carrier.
3. The catalyst in the process for producing 1, 5-pentanediol through the hydroring opening of biological furfuryl alcohol according to claim 2, wherein the SiO in the MFI structure molecular sieve and the FAU structure molecular sieve is SiO2/Al2O3The molar ratio is 18-130.
4. The catalyst in the process for producing 1, 5-pentanediol through the hydroring opening of biological furfuryl alcohol according to claim 2, wherein SiO in the TS-1 molecular sieve2/TiO2The molar ratio is 40-100.
5. The catalyst in the process for producing 1, 5-pentanediol through the hydroring opening of biological furfuryl alcohol according to claim 1, wherein the loading amount of MOx in the catalyst is 0-25%, and the loading amount of M or M' is 0-25%.
6. The catalyst in the process for producing 1, 5-pentanediol through the hydroring opening of bio-furfuryl alcohol according to claim 5, wherein the sum of the loading amounts of MOx and M or M' in the catalyst is 5% -15%.
7. The preparation method of the catalyst in the process for producing 1, 5-pentanediol through the hydroring opening of biological furfuryl alcohol according to any one of claims 1 to 6, wherein the catalyst is prepared by an impregnation method; the impregnation method comprises an excess impregnation method, an equal-volume impregnation method and a plurality of step-by-step impregnation methods.
8. The method for preparing the catalyst in the process for producing 1, 5-pentanediol by the hydrogen ring opening of the bio-furfuryl alcohol according to claim 7, wherein the impregnation method comprises the following steps:
preparation of MOx-M/protonic acid catalyst: dissolving soluble salt of M in deionized water to prepare solution with a certain concentration, adding a powder type carrier according to a metering ratio for impregnation, standing and aging for 6-10h, drying at 100 ℃ for 12h, roasting at 500-600 ℃ for 3-6 h, and tabletting for molding;
preparation of MOx-M'/protonic acid catalyst: respectively preparing soluble salt solutions of M and M' with certain concentrations, uniformly mixing according to a metering ratio, soaking on carrier powder, standing and aging for 6-10h, drying at 100 ℃ for 12h, roasting at 500-600 ℃ for 3-6 h, and tabletting for molding.
9. The application method of the catalyst in the process for producing 1, 5-pentanediol through the hydroring opening of biological furfuryl alcohol according to any one of claims 1 to 6, wherein the catalyst is applied to a high-pressure reaction kettle or a fixed bed reactor; the activation conditions of the catalyst before use were: the partial pressure of the reduced hydrogen is 0.1-4MPa, the reduction temperature is 200-450 ℃, and the reduction time is 2-6 hours; the reaction conditions of the catalyst applied to the fixed bed reactor are as follows: ethanol is used as a solvent, the mass concentration of the furfuryl alcohol solution is 2-100%, the reaction temperature is 100-200 ℃, and the hydrogen pressure is 1-6 MPa.
10. The application method of the catalyst in the process of producing 1, 5-pentanediol through the hydrogen ring opening of bio-furfuryl alcohol as claimed in claim 9, wherein the partial pressure of reducing hydrogen under the activation condition is 1-3MPa, the reducing temperature is 250-350 ℃, and the reducing time is 3-5 hours; the reaction temperature of the reaction conditions is 120-160 ℃, and the hydrogen pressure is 2-4 MPa.
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| CN116920854A (en) * | 2023-06-08 | 2023-10-24 | 山东一诺生物质材料有限公司 | Catalyst, preparation method and production method of 1, 2-pentanediol |
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