CN111215079B - Method for preparing alcohol by hydrogenation of aldehydes by adopting nickel-based heterogeneous catalyst - Google Patents
Method for preparing alcohol by hydrogenation of aldehydes by adopting nickel-based heterogeneous catalyst Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 59
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 41
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000002638 heterogeneous catalyst Substances 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 31
- 150000001299 aldehydes Chemical class 0.000 title description 48
- 238000006243 chemical reaction Methods 0.000 claims abstract description 89
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000001257 hydrogen Substances 0.000 claims abstract description 32
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 32
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 150000001298 alcohols Chemical class 0.000 claims abstract description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000008569 process Effects 0.000 claims abstract description 11
- 239000012876 carrier material Substances 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 3
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 3
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims abstract 16
- 239000007789 gas Substances 0.000 claims description 24
- 239000012263 liquid product Substances 0.000 claims description 24
- 239000000047 product Substances 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 230000003213 activating effect Effects 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 5
- 238000000746 purification Methods 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract 2
- 239000003054 catalyst Substances 0.000 description 53
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 44
- 230000009467 reduction Effects 0.000 description 28
- 238000004817 gas chromatography Methods 0.000 description 18
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 17
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 16
- 238000002360 preparation method Methods 0.000 description 16
- 150000002431 hydrogen Chemical class 0.000 description 15
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- FXHGMKSSBGDXIY-UHFFFAOYSA-N heptanal Chemical compound CCCCCCC=O FXHGMKSSBGDXIY-UHFFFAOYSA-N 0.000 description 8
- 239000006227 byproduct Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- MMFCJPPRCYDLLZ-CMDGGOBGSA-N (2E)-dec-2-enal Chemical compound CCCCCCC\C=C\C=O MMFCJPPRCYDLLZ-CMDGGOBGSA-N 0.000 description 4
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 4
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 4
- MMFCJPPRCYDLLZ-UHFFFAOYSA-N dec-2-enal Natural products CCCCCCCC=CC=O MMFCJPPRCYDLLZ-UHFFFAOYSA-N 0.000 description 4
- 238000009776 industrial production Methods 0.000 description 4
- FWWQKRXKHIRPJY-UHFFFAOYSA-N octadecanal Chemical compound CCCCCCCCCCCCCCCCCC=O FWWQKRXKHIRPJY-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- HSJKGGMUJITCBW-UHFFFAOYSA-N 3-hydroxybutanal Chemical compound CC(O)CC=O HSJKGGMUJITCBW-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- BGEHHAVMRVXCGR-UHFFFAOYSA-N tridecanal Chemical compound CCCCCCCCCCCCC=O BGEHHAVMRVXCGR-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 238000012645 aldehyde polymerization Methods 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
-
- B01J35/615—
-
- B01J35/633—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
- C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention belongs to the field of heterogeneous catalytic reaction processes, and particularly relates to a method for preparing alcohols by hydrogenation of aldehydes by using a nickel-based heterogeneous catalyst. A method for preparing alcohol by aldehyde hydrogenation is characterized in that a nickel-based heterogeneous catalyst is adopted, the main components of the nickel-based heterogeneous catalyst are Ni, mg, na, a selectivity improving agent and an ammonia-treated carrier material, the selectivity improving agent is selected from one of Co, ca, sr and Ba metal elements, the ammonia-treated carrier material is selected from one of ammonia-treated alumina, silica and diatomite, and the method comprises the step of enabling an aldehyde raw material and hydrogen to carry out the aldehyde hydrogenation reaction in a reactor in the presence of the nickel-based heterogeneous catalyst. The method uses the novel nickel-based heterogeneous catalyst, has simple reaction process and device, reduces the subsequent purification and separation cost of alcohol products, effectively improves the economic benefit of the reaction process for producing the alcohol by hydrogenating the aldehydes, and has wide process application prospect.
Description
Technical Field
The invention belongs to the field of heterogeneous catalytic reaction processes, and particularly relates to a method for preparing alcohols by hydrogenation of aldehydes by using a nickel-based heterogeneous catalyst.
Background
The reaction for preparing alcohol by catalytic hydrogenation of aldehyde is the most important catalytic reaction for organic chemical synthesis in laboratories and industrial production, and the aldehyde raw material is prepared into alcohol products by gaseous hydrogen and a heterogeneous catalyst. China also makes some breakthroughs in the aspect of catalytic hydrogenation technologies, and the technologies not only have important functions in further processing and treatment of petroleum, but also are more and more widely applied in fine chemical engineering. However, many catalytic hydrogenation processes still use the technology behind in the fifty years, which has a great gap with the developed countries. The core of the improvement of catalytic hydrogenation technology is to improve the framework of the catalyst. The quality of the catalyst is related to the quality of the whole reaction efficiency, and the good catalyst can realize the process under the conditions of lower energy consumption, less pollution, safety and reliability.
The aldehyde hydrogenation reaction has high requirements on the conversion rate of raw material aldehyde and the selectivity of product alcohol, and in order to reduce the amount of aldehyde returned to the reactor for secondary hydrogenation and the amount of impurities such as esters and ethers generated by side reactions and improve the yield of target product alcohol, the aldehyde hydrogenation catalyst must have high hydrogenation activity and hydrogenation selectivity, and generally requires that the conversion rate of raw material aldehyde is not less than 98% and the selectivity of product alcohol is not less than 98%.
The nickel-based catalyst is widely applied to the field of aldehyde hydrogenation due to the characteristics of high hydrogenation activity, low temperature and low operation energy consumption. In the early process for preparing butanol and octanol by using high-pressure method, ni series catalyst is mostly used for liquid phase hydrogenation, the operation pressure is higher, and with the development of chemical industry, a series of aldehydes medium-pressure hydrogenation catalysts using Ni as main active component are developed in sequence before and after 1990.
Many colleges and universities, scientific research institutions, companies and the like have studied aldehyde hydrogenation catalysts. Ni series Ni-ZrO/SiO introduced in Germany Hoechst company patent EP421196 2 The aldehyde hydrogenation catalyst, ni series aldehyde hydrogenation catalyst introduced in another patent CN1045548C of the same company, adopts alkaline earth metal Mg as an auxiliary agent, can be used for the reaction of preparing n-propanol by hydrogenating propionaldehyde, and the hydrogenation product contains 0.7 percent of unconverted aldehyde and a small amount of by-products. The hydrogenation catalyst for aldehydes of Ni series, which is described in DE43100538 of BASF, contains Zr as a third component and Mo as a fourth component in addition to Cu. The Ni series aldehyde hydrogenation catalyst mentioned in German Huels company patent EP394842 is added with Cu as a first auxiliary agent and Cr as a second auxiliary agent. The Russian Gurevich Gs patent EP326674 describes two stepsThe process and catalyst for producing butanol and octanol by the method are characterized in that Cr is added into a Ni series liquid phase hydrofining catalyst as an auxiliary agent. The propionaldehyde hydrogenation in CN100590108C is a gas phase hydrogenation on a copper-zinc catalyst, the main weight composition of which is 29.4% -50% of copper oxide and 49.4% -70% of zinc oxide, and in CN100564338C, the crude product hydrogenated by using the catalyst contains 0.3% -4% of propyl propionate byproduct.
The method for synthesizing alcohol by aldehyde hydrogenation provided in the above patent has versatility, and has disadvantages that the low temperature reaction activity of aldehyde hydrogenation is not ideal, or by-products such as esters and ethers are generated when the product alcohol is prepared by aldehyde hydrogenation. The aldehyde hydrogenation catalyst needs to have excellent low-temperature reaction activity, the high reaction temperature is easy to cause the generation of raw material aldehyde polymerization and aldol polycondensation reaction, the selectivity of product alcohol is reduced, and the problems of pipeline blockage of industrial production devices and the like are easily caused. Although the amount of the esters and ethers as by-products in the aldehyde hydrogenation reaction is small, the rectification of the main product alcohol is involved in the production process, especially for the ether by-products, the separation of the ether products from the main alcohol product is very difficult, and the required equipment investment and energy consumption are large. It is important that the reaction for preparing alcohol by aldehyde hydrogenation has excellent low-temperature activity and product alcohol selectivity. Therefore, the novel nickel-based heterogeneous catalyst is used, the reaction process and the device are simple, the catalyst has excellent low-temperature activity and product alcohol selectivity, the subsequent purification and separation cost of alcohol products is reduced, the economic benefit of the reaction process for producing alcohol by aldehyde hydrogenation is effectively improved, and the catalyst has wide industrial application prospect.
Disclosure of Invention
In view of the defects in the prior art, the invention aims to provide a reaction process for preparing alcohol by hydrogenation of aldehydes, which can be easily realized industrially and adopts a nickel-based heterogeneous catalyst with excellent low-temperature activity and alcohol selectivity.
The invention provides a method for preparing alcohol by aldehyde hydrogenation, which is characterized in that a nickel-based heterogeneous catalyst is adopted in the method, the main components of the nickel-based heterogeneous catalyst are Ni, mg, na, a selectivity improver and an ammonia-treated carrier material, the selectivity improver is selected from one of Co, ca, sr and Ba metal elements, the ammonia-treated carrier material is selected from one of ammonia-treated alumina, silica and diatomite, and the method comprises the step of carrying out aldehyde hydrogenation reaction on aldehyde raw materials and hydrogen in a reactor in the presence of the nickel-based heterogeneous catalyst.
In a preferred embodiment, the aldehyde starting material is C 2 -C 18 One or a mixture of several aldehydes, and the molar ratio of the hydrogen feed to the aldehyde feed is 5.
In a preferred embodiment, said C 2 -C 18 The aldehyde raw material is conveyed into a reaction system by a high-pressure pump, and the liquid hourly space velocity is 0.1-10h -1 (ii) a The hydrogen raw material is fed in a gas form with a diameter, and the gas space velocity is 500-20000h -1 。
In a preferred embodiment, the reactor is a trickle bed or tank reactor.
In a preferred embodiment, the hydrogenation of aldehydes to alcohols is carried out in a continuous or batch manner.
In a preferred embodiment, the reaction temperature of the reaction for preparing the alcohol by hydrogenating the aldehyde is 60-300 ℃, and the reaction pressure is 0.05-20MPa.
In a preferable embodiment, the mass contents of Ni, mg and Na in the nickel-based heterogeneous catalyst are respectively 40% -70%, 2% -10% and 0.5% -5%, and the mass content of the selectivity improver is 0.1% -5%.
In a preferred embodiment, the nickel-based heterogeneous catalyst is a cylinder having a diameter of 3mm to 6mm and a height of 3mm to 6mm, and has a bulk density of 0.6 to 1.6g/cm 3 The specific surface area is 100-300m 2 Per g, pore volume of 0.2-0.5cm 3 /g。
In a preferred embodiment, the ammonia-treated support material is one which has been treated with ammonia at a temperature of from 300 to 500 ℃ and a gas space velocity of from 200 to 2000h -1 And activating the carrier material by ammonia gas under the condition of treatment time of 4-20 h.
In a preferred embodiment, when the reactor is a trickle bed, the aldehyde hydrogenation to alcohols reaction is carried out continuously over the nickel-based heterogeneous catalyst, and the resulting liquid product continuously flows out of the reactor and is collected by a product collection tank at a temperature of-20 to 25 ℃; when the reactor is a kettle type reactor, the reaction for preparing the alcohol by aldehyde hydrogenation is carried out intermittently, the generated liquid product is obtained by filtering and separating from the nickel-based heterogeneous catalyst, and the obtained liquid product is further processed by rectification or flash evaporation to obtain the alcohol product with high purity.
The benefits of the present invention include, but are not limited to, the following: compared with the prior reaction technology for preparing alcohol by aldehyde hydrogenation, the novel nickel-based heterogeneous catalyst is adopted, so that the excellent low-temperature activity and alcohol selectivity of the hydrogenation reaction are ensured, and the economic cost of subsequent purification and separation of alcohol products is greatly reduced; wide range of reaction substrates, suitable for C 2 -C 18 Hydrogenation of aldehydes; the reaction process has mild conditions; the preparation method of the catalyst is simple, and the characteristics improve the economic benefit of the reaction process for producing alcohols by aldehyde hydrogenation and are suitable for the application of industrial production devices for producing alcohols by aldehyde hydrogenation.
Drawings
FIG. 1 is a reaction scheme of a continuously performed reaction for hydrogenating aldehydes to alcohols according to the present invention.
Detailed Description
In order to better illustrate the preparation of the catalyst and its use in the hydrogenation of aldehydes to alcohols, some examples of the preparation of catalyst samples and their use in the reaction process are given below, but the present invention is not limited to the examples. Unless otherwise specifically stated, the contents and percentages in the present application are calculated as "mass".
Example 1
Under the reaction condition of 100 ℃, 95g of Ni (NO) is added 3 ) 2 ·6H 2 O、17.8g Mg(NO 3 ) 2 ·6H 2 O、3.69g Co(NO 3 ) 2 ·6H 2 O was dissolved in 0.5 liter of boiling water. 75g of Na were added in a stirred reactor at 100 ℃ under reaction conditions 2 CO 3 Dissolved in 0.7 liter of boiling water. Quick-acting toolUnder the condition of quick stirring, ni (NO) is added 3 ) 2 -Mg(NO 3 ) 2 -Co(NO 3 ) 2 The solution was poured into Na at a rate of 5 ml/sec 2 CO 3 In solution. After the Ni-Mg-Co solution was poured, 11.5g of the diatomaceous earth powder which had been subjected to the ammonia treatment was rapidly added, and the reaction mixture was stirred for 5 minutes. After filtration, the filter cake was washed with hot water at 80 ℃ and the conductivity of the effluent washing water was measured, and the washing was stopped when the conductivity had decreased to 1800. Mu.s. The filter cake was placed in 0.3 l of 0.25wt% NaOH solution under 50 ℃ reaction conditions, and the reaction suspension was stirred for 3 hours. Then filtering, putting the filter cake into a drying oven, drying for 5 hours at 60 ℃, 5 hours at 80 ℃ and 10 hours at 120 ℃ to constant weight. The catalyst is prepared through the procedures of granulation and tabletting. In the preparation method of the catalyst, the kieselguhr powder subjected to ammonia treatment is mentioned, wherein the ammonia treatment refers to the reaction temperature of 500 ℃ and the gas space velocity of 1000h -1 And the ammonia treatment time is 10h.
Adding the prepared novel nickel-based heterogeneous catalyst into a trickle bed reactor, introducing hydrogen, wherein the reduction temperature of the catalyst is 425 ℃, the reduction time is 4h, the reduction pressure is 0.5MPa, and the space velocity of the reduction gas is 1000h -1 . After the catalyst is reduced by hydrogen, the raw material propionaldehyde is pumped into a reactor by a high-pressure metering pump to start reaction, the propionaldehyde hydrogenation reaction temperature is 125 ℃, the reaction pressure is 1.2MPa, and the propionaldehyde liquid hourly space velocity is 1.5h -1 Hydrogen/propanal molar ratio 90. Collecting the liquid product n-propanol in a cold trap collecting tank. The liquid product was analyzed by HP-7890N gas chromatography equipped with an HP-5 capillary column and a FID detector, using sec-butanol as internal standard. The reaction off-gas was analyzed on-line using HP-7890N gas chromatography equipped with Porapak-QS column and TCD detector. The reaction results are shown in Table 1.
Example 2
Preparation of the catalyst see example 1, except that 2.98g Ca (NO) was used in the catalyst preparation 3 ) 2 ·4H 2 O instead of 3.69g Co (NO) 3 ) 2 ·6H 2 O, catalyst preparation the other procedures were the same as in example 1.
Adding the prepared novel nickel-based heterogeneous catalyst into a trickle bed reactor, and introducingHydrogen, the reduction temperature of the catalyst is 425 ℃, the reduction time is 4h, the reduction pressure is 0.5MPa, and the space velocity of the reduction gas is 1000h -1 . After the catalyst is reduced by hydrogen, the raw material propionaldehyde is pumped into a reactor by a high-pressure metering pump to start reaction, the propionaldehyde hydrogenation reaction temperature is 125 ℃, the reaction pressure is 1.2MPa, and the propionaldehyde liquid hourly space velocity is 1.5h -1 Hydrogen/propanal molar ratio 90. Collecting the liquid product n-propanol in a cold trap collecting tank. The liquid product was analyzed by HP-7890N gas chromatography equipped with an HP-5 capillary column and a FID detector, using sec-butanol as internal standard. The reaction off-gas was analyzed on-line using HP-7890N gas chromatography equipped with a Porapak-QS column and a TCD detector. The reaction results are shown in Table 1.
Example 3
The catalyst preparation process is the same as in example 1 except that in the ammonia treatment step for catalyst preparation, the reaction temperature is 300 ℃ instead of 500 ℃ and the ammonia treatment time is 4h instead of 10h, in example 1.
Adding the prepared novel nickel-based heterogeneous catalyst into a trickle bed reactor, introducing hydrogen, wherein the reduction temperature of the catalyst is 425 ℃, the reduction time is 4h, the reduction pressure is 0.5MPa, and the airspeed of the reduction gas is 1000h -1 . After the catalyst is reduced by hydrogen, the raw material propionaldehyde is pumped into a reactor by a high-pressure metering pump to start reaction, the propionaldehyde hydrogenation reaction temperature is 125 ℃, the reaction pressure is 1.2MPa, and the propionaldehyde liquid hourly space velocity is 1.5h -1 Hydrogen/propanal molar ratio 90. Collecting the liquid product n-propanol in a cold trap collecting tank. The liquid product was analyzed by HP-7890N gas chromatography equipped with an HP-5 capillary column and a FID detector, using sec-butanol as internal standard. The reaction off-gas was analyzed on-line using HP-7890N gas chromatography equipped with a Porapak-QS column and a TCD detector. The reaction results are shown in Table 1.
Example 4
See example 1 for the preparation of the catalyst.
Adding the prepared novel nickel-based heterogeneous catalyst into a trickle bed reactor, introducing hydrogen, wherein the reduction temperature of the catalyst is 425 ℃, the reduction time is 4h, the reduction pressure is 0.5MPa, and the airspeed of the reduction gas is 1000h -1 . After the catalyst is reduced by hydrogen, the raw materialPumping propionaldehyde into a reactor through a high-pressure metering pump to start reaction, wherein the propionaldehyde hydrogenation reaction temperature is 100 ℃, the reaction pressure is 0.35MPa, and the propionaldehyde liquid hourly space velocity is 1.5h -1 Hydrogen/propanal molar ratio 90. Collecting the liquid product n-propanol in a cold trap collecting tank. The liquid product was analyzed by HP-7890N gas chromatography equipped with an HP-5 capillary column and a FID detector, using sec-butanol as internal standard. The reaction off-gas was analyzed on-line using HP-7890N gas chromatography equipped with Porapak-QS column and TCD detector. The reaction results are shown in Table 1.
Example 5
See example 1 for the preparation of the catalyst.
Adding the prepared novel nickel-based heterogeneous catalyst into a trickle bed reactor, introducing hydrogen, wherein the reduction temperature of the catalyst is 425 ℃, the reduction time is 4h, the reduction pressure is 0.5MPa, and the airspeed of the reduction gas is 1000h -1 . After the catalyst is reduced by hydrogen, the raw material propionaldehyde is pumped into a reactor by a high-pressure metering pump to start reaction, the propionaldehyde hydrogenation reaction temperature is 125 ℃, the reaction pressure is 1.2MPa, and the propionaldehyde liquid hourly space velocity is 1.5h -1 Hydrogen/propanal molar ratio 10. Collecting the liquid product n-propanol in a cold trap collecting tank. The liquid product was analyzed by HP-7890N gas chromatography equipped with an HP-5 capillary column and a FID detector, using sec-butanol as internal standard. The reaction off-gas was analyzed on-line using HP-7890N gas chromatography equipped with Porapak-QS column and TCD detector. The reaction results are shown in Table 1.
Example 6
See example 1 for the preparation of the catalyst.
Adding the prepared novel nickel-based heterogeneous catalyst into a trickle bed reactor, introducing hydrogen, wherein the reduction temperature of the catalyst is 425 ℃, the reduction time is 4h, the reduction pressure is 0.5MPa, and the space velocity of the reduction gas is 1000h -1 . After the catalyst is reduced by hydrogen, the raw material n-heptanal is pumped into a reactor by a high-pressure metering pump to start reaction, the hydrogenation reaction temperature of the n-heptanal is 125 ℃, the reaction pressure is 2.0MPa, and the hourly space velocity of the n-heptanal liquid is 1.0h -1 The hydrogen/n-heptanal molar ratio was 30. The liquid product n-heptanol is collected in a cold trap collection tank. The liquid product was analyzed by HP-7890N gas chromatography using an HP-5 capillary column and FID detector, using sec-butanolAs an internal standard. The reaction off-gas was analyzed on-line using HP-7890N gas chromatography equipped with a Porapak-QS column and a TCD detector. The reaction results are shown in Table 1.
Example 7
See example 1 for the preparation of the catalyst.
Adding the prepared novel nickel-based heterogeneous catalyst into a trickle bed reactor, introducing hydrogen, wherein the reduction temperature of the catalyst is 425 ℃, the reduction time is 4h, the reduction pressure is 0.5MPa, and the airspeed of the reduction gas is 1000h -1 . After the catalyst is reduced by hydrogen, pumping the raw material decenal into a reactor through a high-pressure metering pump to start reaction, wherein the hydrogenation reaction temperature of the decenal is 135 ℃, the reaction pressure is 3.0MPa, and the hourly space velocity of the decenal liquid is 0.5h -1 Hydrogen/decenal molar ratio 30. Collecting the liquid product decanol in a cold trap collection tank. The liquid product was analyzed by HP-7890N gas chromatography equipped with an HP-5 capillary column and a FID detector, using sec-butanol as internal standard. The reaction off-gas was analyzed on-line using HP-7890N gas chromatography equipped with a Porapak-QS column and a TCD detector. The reaction results are shown in Table 1.
Example 8
See example 1 for the preparation of the catalyst.
Adding the prepared novel nickel-based heterogeneous catalyst into an autoclave reactor, weighing 5g of tridecanal and 5g of toluene, placing the weighed materials into the autoclave reactor, sealing the reactor, carrying out an air tightness test, introducing hydrogen, replacing air in the reactor for 5 times, continuously flushing the hydrogen at the reaction temperature of 135 ℃ and the reaction pressure of 3MPa, and starting reaction under the condition that the reaction pressure is kept unchanged and the stirring revolution number of the autoclave is 500 revolutions per minute. After the reaction is carried out for 1 hour, the reaction kettle is opened, the liquid product is extracted from the high-pressure kettle reactor, and the catalyst can be left in the reaction kettle for recycling. The liquid product was analyzed by HP-7890N gas chromatography equipped with an HP-5 capillary column and a FID detector, using sec-butanol as internal standard. The reaction off-gas was analyzed on-line using HP-7890N gas chromatography equipped with Porapak-QS column and TCD detector. The reaction results are shown in Table 1.
Example 9
See example 1 for the preparation of the catalyst.
Adding the prepared novel nickel-based heterogeneous catalyst into an autoclave reactor, weighing 5g of n-octadecanal and 5g of toluene, placing the n-octadecanal and the 5g of toluene into the autoclave reactor, sealing the reactor, carrying out an air-tight test, introducing hydrogen, replacing air in the reactor for 5 times, continuously flushing the hydrogen at the reaction temperature of 135 ℃ and the reaction pressure of 3MPa, and starting reaction under the condition that the reaction pressure is kept unchanged and the stirring revolution number of the autoclave is 500 revolutions per minute. After the reaction is carried out for 1 hour, the reaction kettle is opened, the liquid product is extracted from the autoclave reactor, and the catalyst can be left in the reaction kettle for recycling. The liquid product was analyzed by HP-7890N gas chromatography equipped with an HP-5 capillary column and a FID detector, using sec-butanol as internal standard. The reaction off-gas was analyzed on-line using HP-7890N gas chromatography equipped with Porapak-QS column and TCD detector. The reaction results are shown in Table 1.
TABLE 1 reaction performance of aldehyde hydrogenation to alcohol on novel Ni-based multiphase catalyst
The results show that the method for preparing the alcohol by the aldehyde hydrogenation by using the nickel-based heterogeneous catalyst ensures the excellent low-temperature activity and alcohol selectivity of the hydrogenation reaction, and greatly reduces the economic cost for subsequent purification and separation of the alcohol product; wide range of reaction substrates, suitable for C 2 -C 18 Hydrogenation of aldehydes; the reaction process has mild conditions; the preparation method of the catalyst is simple, and the characteristics improve the economic benefit of the reaction process for producing the alcohols by aldehyde hydrogenation and are suitable for the application of industrial production devices for producing the alcohols by aldehyde hydrogenation.
The present invention has been described in detail above, but the present invention is not limited to the specific embodiments described herein. It will be understood by those skilled in the art that other modifications and variations may be made without departing from the scope of the invention. The scope of the invention is defined by the appended claims.
Claims (8)
1. A method for using nickel-based heterogeneous catalyst to be used for aldehyde hydrogenation to alcohol reaction is characterized in that the nickel-based heterogeneous catalyst mainly comprises Ni, mg, na, selectivity improver and ammonia-treated carrier material, wherein the selectivity improver is one or more than two of Co, ca, sr and Ba metal elements, the ammonia-treated carrier material is one of ammonia-treated silicon dioxide and diatomite, and the method comprises the steps of enabling an aldehyde raw material and hydrogen to carry out aldehyde hydrogenation reaction in a reactor in the presence of the nickel-based heterogeneous catalyst; the mass contents of Ni, mg and Na in the nickel-based heterogeneous catalyst are respectively 40-70%, 2-10% and 0.5-5%, and the mass content of the selectivity improver is 0.1-5%; the ammonia treatment of the carrier material is carried out at the temperature of 300-500 ℃ and the gas space velocity of 200-2000h -1 And activating the carrier material by ammonia gas under the condition of treatment time of 4-20 h.
2. The method according to claim 1, wherein the aldehyde raw material is C 2 -C 18 One or a mixture of several aldehydes, and the molar ratio of the hydrogen feed to the aldehyde feed is 5.
3. The method of claim 1, wherein C is 2 -C 18 The aldehyde raw material is conveyed into a reaction system by a high-pressure pump, and the liquid hourly space velocity is 0.1-10h -1 (ii) a The hydrogen raw material is fed in a gas form with a diameter, and the gas space velocity is 500-20000h -1 。
4. A process according to claim 1, 2 or 3, wherein the reactor is a trickle bed or tank reactor.
5. The process according to claim 1, wherein the hydrogenation of the aldehydes to alcohols is carried out continuously or batchwise.
6. The process according to claim 1, 2 or 3, wherein the reaction temperature of the reaction for preparing alcohols by hydrogenating aldehydes is 60 to 300 ℃ and the reaction pressure is 0.05 to 20MPa.
7. The process according to claim 1, wherein the nickel-based heterogeneous catalyst is a cylinder having a diameter of 3mm to 6mm and a height of 3mm to 6mm and a bulk density of 0.6 to 1.6g/cm 3 The specific surface area is 100-300m 2 Per g, pore volume of 0.2-0.5cm 3 /g。
8. The process of claim 4, wherein when the reactor is a trickle bed reactor, the aldehyde hydrogenation to alcohols is continuously conducted over the nickel-based heterogeneous catalyst, and the resulting liquid product continuously flows out of the reactor and is collected by a product collection tank at a temperature of-20 to 25 ℃;
when the reactor is a kettle type reactor, the reaction for preparing the alcohol by hydrogenating the aldehydes is carried out intermittently, the generated liquid product is obtained by filtering and separating from the nickel-based heterogeneous catalyst, and the obtained liquid product is further processed by rectification or flash evaporation to obtain the alcohol product with high purity.
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