阅读说明：本技术 一种由丁烯齐聚物制备高碳醇的方法 (Method for preparing high-carbon alcohol from butene oligomer ) 是由 姜淼 丁云杰 严丽 王国庆 程显波 金明 于 2020-05-26 设计创作，主要内容包括：本发明涉及一种由丁烯齐聚物制备高碳醇的方法,所述反应以丁烯齐聚物为原料,在催化剂的作用下,经两步法合成高碳醇。本发明包括以下步骤：1)原料丁烯齐聚物与合成气在氢甲酰化多相催化剂上反应生成高碳醛；2)高碳醛继续反应,在加氢催化剂上发生醛加氢反应生成目标产物高碳醇。本发明方法反应工艺简单易行,适用于大规模工业化生产,反应活性和选择性优异,反应稳定性良好；氢甲酰化反应采用新型固体多相催化剂,降低了催化剂同反应物和产物的分离成本。利用本发明方法可以通过价廉易得的丁烯齐聚物制备高附加值化学品高碳醇,工业应用前景广阔。(The invention relates to a method for preparing high-carbon alcohol from butylene oligomer, which takes butylene oligomer as raw material to synthesize the high-carbon alcohol through a two-step method under the action of a catalyst. The invention comprises the following steps: 1) the raw material butylene oligomer and synthesis gas react on a hydroformylation heterogeneous catalyst to generate high-carbon aldehyde; 2) the high carbon aldehyde continues to react, and aldehyde hydrogenation reaction is carried out on the hydrogenation catalyst to generate the target product high carbon alcohol. The method has simple and easy reaction process, is suitable for large-scale industrial production, and has excellent reaction activity and selectivity and good reaction stability; the hydroformylation reaction adopts a novel solid heterogeneous catalyst, so that the separation cost of the catalyst, reactants and products is reduced. The method can prepare high-added-value chemical high-carbon alcohol by cheap and easily-obtained butylene oligomers, and has wide industrial application prospect.)

1. A method for preparing high-carbon alcohol by butylene oligomer is characterized in that butylene oligomer, synthetic gas and hydrogen are used as raw materials, and a target product, namely high-carbon alcohol, is generated through hydroformylation reaction and hydrogenation reaction in two steps; the method comprises the following two steps: 1) the raw material butylene oligomer and synthesis gas react on a hydroformylation heterogeneous catalyst to generate high-carbon aldehyde (the carbon number is more than or equal to 8); 2) the high carbon aldehyde continues to react, and aldehyde hydrogenation reaction is carried out on the hydrogenation catalyst to generate the target product high carbon alcohol (the carbon number is more than or equal to 8).

2. The method according to claim 1, wherein the butene is one or more of 1-butene, 2-butene or isobutene, and the butene oligomer is one or more of products obtained after dimerization, trimerization or tetramerization of one or more of the butenes.

3. The method of claim 1, wherein the hydroformylation catalyst is a solid heterogeneous catalyst, and is composed of a metal component and an organic phosphine ligand polymer, wherein the metal component is one or more of Rh, Co or Ir, the organic phosphine ligand polymer is a polymer generated by solvent thermal polymerization of one or more of organic phosphine ligands containing vinyl, and the functionalized phosphine ligand is one or more of the following compounds:

4. the process according to claim 1 or 3, characterized in that the hydroformylation solid heterogeneous catalyst consists of a metal component and an organophosphine ligand polymer, the metal active component constituting from 0.005% to 20.0% (preferably from 0.1% to 10.0%) by weight of the total solid heterogeneous catalyst,

the specific surface area of the organic phosphine ligand polymer is 100-3000m²(preferably 500-²Per g), pore volume of 0.1-5.0cm³Per g (preferably 1.0-3.0 cm)³(g), a pore size distribution of 0.1 to 200.0nm (preferably 0.15 to 100.0nm), and a thermal polymerization temperature of the polymer solvent of 323-473K.

5. The process of claim 1, wherein the aldehyde hydrogenation catalyst comprises the following main components: the main components take Ni, Cu, Mg and Na as active components, take a selectivity improver as an auxiliary agent and take a carrier material treated by ammonia as a carrier;

the selectivity improver is selected from one or more of Co, Ca, Sr or Ba metal elements;

the carrier material subjected to ammonia treatment is selected from one or more of alumina, silicon dioxide and kieselguhr subjected to ammonia treatment;

the hydrogenation catalyst contains Ni, Cu, Mg and Na with the mass content of 30-60% (preferably 35-55%), 2-18% (preferably 5-15%), 2-10% (preferably 4-8%), 0.5-5% (preferably 1-4%), a selectivity improver with the mass content of 0.1-5% (preferably 0.2-4%) and the balance of a carrier.

6. The method of claim 5,

the bulk density of the hydrogenation catalyst is 0.5-2.0g/cm³The specific surface area is 100-500m²Per g, pore volume of 0.2-0.8cm³/g；

The ammonia treatment refers to that the carrier material is at the temperature of 573-^-1(preferably 400-^-1) And activating the treated carrier material by ammonia gas under the condition of 4-20h (preferably 6-16h) of treatment time.

7. The process according to claim 1 or 2, characterized in that the hydroformylation reaction conditions are: the reaction temperature is 293-573K (preferably 323-523K), and the reaction pressure is 0.1-20.0MPa (preferably 0.2-10.0 MP)a) Gas volume space velocity of 100-^-1(preferably 500-10000 h)^-1) Liquid volume space velocity of 0.01-10.0h^-1(preferably 0.05-8.0 h)^-1) The mol ratio of the butylene oligomer in the raw material to the CO in the synthetic gas is 0.001:1-10:1 (preferably 0.01:1-5:1), and the butylene oligomer in the raw material and the H in the synthetic gas₂In a molar ratio of 0.001:1 to 10:1 (preferably 0.01:1 to 5: 1).

8. The method according to claim 1 or 2, wherein in the hydroformylation reaction, the synthetic gas is one or more than two of gas making processes taking natural gas, coal, oil field gas, coal bed gas or hydrocarbon as raw materials, and the main component of the synthetic gas is H₂And CO as an impurity₂、CH₄Etc. H₂And CO in an amount of 20% to 100% (preferably 50% to 100%) by volume, H₂The volume/CO ratio is between 0.5 and 5.0 (preferably between 0.8 and 4.0).

9. The process according to claim 1 or 2, characterized in that the aldehyde hydrogenation reaction conditions are: the reduction temperature is 473-773K (preferably 523-723K), the reduction pressure is 0.05-20.0MPa (preferably 0.1-10.0MPa), and the volume space velocity of the reduction hydrogen is 100-20000h^-1(preferably 500-10000 h)^-1) The reaction temperature is 333-573K (preferably 353-523K), the reaction pressure is 0.05-20.0MPa (preferably 0.1-10.0MPa), and the liquid volume space velocity is 0.1-10h^-1(preferably 0.15-8 h)^-1) The gas volume space velocity is 500-20000h^-1(preferably 800-^-1) (ii) a The molar ratio of hydrogen feed to aldehyde feed is from 1:1 to 200:1 (preferably from 2:1 to 150: 1).

Technical Field

The invention relates to a method for preparing high-carbon alcohol from butylene oligomer, belonging to the technical field of heterogeneous catalysis.

Background

With the rapid increase in crude oil processing capacity and the increasing production of ethylene, C, a byproduct of petrochemical industry₄The yield of fractions (n-butenes, butadiene, isobutene, etc.) will increase. At present, compared with ethylene and propylene, the utilization rate and the utilization value of butylene are lower, and most of butylene is used as industrial and civil fuel except that a part of butylene is used for preparing butadiene at home. The butene oligomerization reaction is a typical acid catalysis reaction, and dimers and trimers generated by the oligomerization reaction are very important organic chemical intermediates and can be used for producing long-chain olefins which are in shortage in China. Butene Dimers (DIB) are useful as gasoline blending components and also as relative molecular mass modifiers for the production of polyisobutylene. Butene Trimer (TRIB) is useful for producing detergents, lubricating oils and perfumes, or for synthesizing polymer relative molecular mass regulators, agricultural emulsifiers and the like.

At present, the production of high-alcohol plasticizers in China is almost blank, and the high-alcohol plasticizers always depend on import, so that the quantity is small, the price is high, and the development and the quality improvement of the plastic processing industry are restricted. The preparation of high-carbon alcohol by hydroformylation and hydrogenation reaction of cheap and easily available butylene oligomer raw materials is a feasible method in industrial production. The core of the method technology is the first step, namely, the butylene oligomer raw material is subjected to hydroformylation reaction to prepare high-carbon aldehyde. At present, the Co catalytic process still plays a key role in the hydroformylation reaction of preparing high-carbon aldehyde/alcohol from long-chain olefin, but due to the factors of harsh reaction conditions, poor selectivity, more side reactions, high energy consumption, complexity in the Co recovery process and the like, the comprehensive economic and technical indexes of the Co-based hydroformylation catalytic process are far inferior to those of the Rh-based catalytic process. Therefore, research on hydroformylation of long-chain olefins using Rh-based catalysts has become one of the hot spots in the research field.

Hydroformylation is a typical atom-economical reaction, and catalytic processes and catalysts thereof have been studied for nearly 60 years. Currently, approximately over 1200 million tons of aldehydes and alcohols are produced worldwide each year using olefin hydroformylation technology. The reaction can generate aldehyde from raw olefin under less harsh conditions, and the product aldehyde can be further hydrogenated and converted into alcohol. The homogeneous catalysis system has higher catalytic activity and selectivity of target products under mild reaction conditions, but the separation problem of the catalyst and reaction materials is difficult, thus hindering large-scale industrial application of the homogeneous catalysis system. Compared with homogeneous catalysis, heterogeneous catalysis has the greatest advantages that the catalyst and reaction materials are easy to separate, and the main problems of the heterogeneous catalysis are harsh reaction conditions, relatively low reaction activity and the like. At present, the main research focus on hydroformylation is on developing a novel heterogeneous catalyst, which not only has the advantage of easy separation of heterogeneous catalytic catalyst and reaction materials, but also has high reaction activity and mild reaction conditions of homogeneous catalysis. In conclusion, the research on the novel Rh-based hydroformylation heterogeneous catalyst is a key step of a reaction process for preparing high-carbon alcohol by using cheap and easily available butene oligomer.

Co catalysis technology from Exxon Mobil is the dominant technology for the production of isononyl alcohol. The process flow is as follows: the mixed octenes are reacted in contact with synthesis gas in a carbonylation reactor at high pressure and unreacted synthesis gas discharged from the carbonylation reactor is recycled and a purge stream is used to control the inert component concentration. Volatile cobalt tetracarbonyl in the crude aldehyde product is first removed, and then water soluble cobalt is washed away with water. And (3) hydrogenating the aldehyde after cobalt removal, removing light and heavy components through 2 series-connected fractionators, and finally performing hydrorefining to obtain the product.

The mixed octene prepared by oligomerization of butene in national laboratory of chemical industry of Qinghua university C1 in China is used as a raw material, and the yield of isononanal reaches 90 percent at 140 ℃ and 10.5MPa by using a rhodium catalyst with triphenylphosphine oxide as a ligand.

U.S. p.6184413 is a patent applied by university of california, reporting a supported phase catalyst whose supported phase is highly polar, such as ethylene glycol or glycerol; the metal center of the catalyst is chiral sulfonated 2, 2-bis (diphenylphosphino) -1, 1-bis (naphthyl) metal complex, the complex can be dissolved in a load phase, and the catalyst system can be used for asymmetric synthesis with optical activity.

Balue et al (J.mol.Catal.A., Chem,1999,137:193-203) use cation exchange resin as a carrier to form a heterogeneous catalyst by immobilizing rhodium sulfur compounds, and the cycle experiment of styrene hydroformylation shows that the heterogeneous catalyst has poor stability and the phenomenon of Rh loss is serious. Zeelie et al (appl.Catal.A: Gen, 2005,285:96-109) modified styrene and p-styrene diphenylphosphine on polyethylene fibers, Rh (acac) (CO)₂The catalyst is anchored on a modified polyethylene fiber, and the ethylene hydroformylation result shows that the catalyst has higher conversion rate but poor stability under the conditions of 100 ℃ and 5bar, the reaction activity is sharply reduced after 50 hours of reaction, and the catalyst deactivation phenomenon is serious.

In summary, the most critical step of the reaction process route of preparing higher alcohols by hydroformylation and hydrogenation of butene oligomers is hydroformylation. At present, the most widely researched Rh-based hydroformylation catalytic reaction system of high-carbon olefin is how to develop a novel Rh-based homogeneous heterogeneous catalytic system with the advantages of homogeneous catalysis and heterogeneous catalysis, and is the main focus of current research.

Disclosure of Invention

In order to solve the above problems, the present invention aims to provide a method for preparing a higher alcohol from a butene oligomer, wherein the butene oligomer is used as a raw material in the reaction, and the higher alcohol is synthesized by a two-step method under the action of a catalyst.

The method takes the butylene oligomer, synthesis gas and hydrogen as raw materials, and generates the target product high-carbon alcohol through two steps of hydroformylation reaction and hydrogenation reaction. The method comprises two steps: 1) the raw material butylene oligomer and synthesis gas react on a hydroformylation heterogeneous catalyst to generate high-carbon aldehyde; 2) the high carbon aldehyde continues to react, and aldehyde hydrogenation reaction is carried out on the hydrogenation catalyst to generate the target product high carbon alcohol.

In a preferred embodiment, the butene is one or more of 1-butene, 2-butene or isobutene, and the butene oligomer is a product obtained after dimerization, trimerization or tetramerization of butene.

In a preferred embodiment, the hydroformylation catalyst is a solid heterogeneous catalyst, and is composed of a metal component and an organic phosphine ligand polymer, wherein the metal component is one or more of Rh, Co or Ir, the organic phosphine ligand polymer is a polymer generated by solvent thermal polymerization of one or more of organic phosphine ligands containing vinyl, and the functionalized phosphine ligand is one or more selected from the following:

in a preferred embodiment, the hydroformylation solid heterogeneous catalyst, the metal active component accounts for 0.005-20.0% of the total weight of the solid heterogeneous catalyst, and the specific surface area of the organic phosphine ligand polymer is 100-3000m²Per g, pore volume of 0.1-5.0cm³(ii)/g, the pore size distribution is 0.1-200.0 nm.

In a preferred embodiment, the main components of the aldehyde hydrogenation catalyst comprise four active components of Ni, Cu, Mg and Na, a selectivity improver as an auxiliary agent, and a carrier material treated by ammonia; the selectivity improver is selected from one or more of Co, Ca, Sr or Ba metal elements; the carrier material subjected to ammonia treatment is selected from one or more of alumina, silicon dioxide and kieselguhr subjected to ammonia treatment; the mass contents of Ni, Cu, Mg and Na in the hydrogenation catalyst are respectively 30-60%, 10-20%, 2-10% and 0.5-5%, and the mass content of the selectivity improver is 0.1-5%.

In a preferred embodiment, the hydrogenation catalyst has a bulk density of from 0.5 to 2.0g/cm³The specific surface area is 100-500m²Per g, pore volume of 0.2-0.8cm³(ii)/g; the ammonia treatment refers to 500 ℃ at the temperature of 300 ℃ and 2000h at the ammonia gas space velocity of 200-^-1Activating the carrier material with ammonia gas for 4-20h。

In a preferred embodiment, the hydroformylation reaction conditions are: the reaction temperature is 293-573K, the reaction pressure is 0.1-20.0MPa, and the gas volume space velocity is 100-20000h^-1Liquid volume space velocity of 0.01-10.0h^-1The mol ratio of the raw material of the butylene oligomer to the synthesis gas is 0.001:1-10: 1.

In a preferred embodiment, in the hydroformylation reaction, the synthesis gas is obtained in a gas making process taking natural gas, coal, oil field gas, coal bed gas or hydrocarbon as raw materials, and the main component of the synthesis gas is H₂And CO, H₂And CO in an amount of 20 to 100% by volume, H₂The volume ratio of/CO is 0.5-5.0.

In a preferred embodiment, the aldehyde hydrogenation reaction conditions are: the reduction temperature is 473-773K, the reduction pressure is 0.05-20.0MPa, and the volume space velocity of the reduction hydrogen is 100-^-1The reaction temperature is 333-573K, the reaction pressure is 0.05-20.0MPa, and the liquid volume space velocity is 0.1-10h^-1The gas volume space velocity is 500-20000h^-1(ii) a The molar ratio of the hydrogen raw material to the aldehyde raw material is 1:1-200: 1.

In a preferred embodiment, the inert gas is Ar, N₂And He is one or more than two of them.

The benefits of the present invention include, but are not limited to, the following: 1) compared with the existing hydroformylation reaction technology applied in industry, the novel solid heterogeneous catalyst is adopted, so that the separation cost of the catalyst, reactants and products is reduced; the reaction process is simple and easy to implement, is suitable for large-scale industrial production, and has excellent reaction activity and selectivity and good reaction stability. 2) In the high-carbon aldehyde hydrogenation reaction, a novel nickel-based heterogeneous catalyst is used, the catalyst has excellent low-temperature activity and alcohol product selectivity, the subsequent purification and separation cost of an alcohol product is reduced, and the economic benefit of the reaction process for producing high-carbon alcohol by hydrogenation of high-carbon aldehyde is effectively improved. The method can prepare the high-added-value chemical high-carbon alcohol from the butylene oligomer through two-step reaction of multiphase hydroformylation and aldehyde hydrogenation, and has higher economic value and wide industrial application prospect.

Drawings

FIG. 1 is a flow diagram of a process for the continuous preparation of higher aldehydes by heterogeneous hydroformylation of butene oligomers according to the present invention. Wherein 1 is hydrogen, 2 is the air-vent valve, 3 is the filter, 4 is the check valve, 5 is fixed bed reactor, 6 is the accumulator tank, 7 is the liquid product, 8 is the back pressure valve, 9 is the gaseous product, 10 is unloading A, 11 is unloading B, 12 is the charge pump, 13 is raw materials storage tank (butene oligomer).

FIG. 2 is a flow chart of a reaction process for preparing higher alcohols by hydrogenation of higher aldehydes, which is continuously carried out according to the present invention. Wherein 1 is hydrogen, 2 is the air-vent valve, 3 is the filter, 4 is the check valve, 5 is fixed bed reactor, 6 is the accumulator tank, 7 is the liquid product, 8 is the back pressure valve, 9 is the gaseous product, 10 is unloading A, 11 is unloading B, 12 is the charge pump, 13 is raw materials storage tank (aldehyde).

Detailed Description

In order to better illustrate the preparation method of the catalyst and the application thereof in preparing high-value chemical high-carbon alcohol from the butene oligomer, the following examples of the preparation of some catalyst samples and the application thereof in the reaction process are given, but the 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

1) Hydroformylation heterogeneous catalyst preparation

Under the protection of 298K and Ar gas, 10.0g of tris (4-vinylphenyl) phosphine ligand is dissolved in 100ml of tetrahydrofuran solvent, 0.25g of free radical initiator azobisisobutyronitrile is added to the solution, and stirring is carried out for 1 h. And transferring the stirred solution into a hydrothermal autoclave, and carrying out solvothermal polymerization for 24h under the protection of 373K and Ar gas. Cooling to room temperature after the polymerization, and removing the solvent in 338K vacuum to obtain the organic phosphine ligand polymer (the specific surface area of which is 1080 m)²G, pore volume of 1.56m³(ii)/g, pore size distribution of 0.12-90.0 nm). 62.65mg of rhodium acetylacetonate dicarbonyl were weighed out and dissolved in 100ml of tetrahydrofuran solvent under the protection of 298K and Ar gas, 5.0g of the phosphine ligand polymer prepared above was added, and stirring was carried out for 24 hours. Subsequently, 338K was evacuatedSolvent, namely, obtaining the solid heterogeneous catalyst with the metal component supported by the phosphine ligand polymer.

2) Butene oligomer hydroformylation reaction process

The prepared hydroformylation heterogeneous catalyst is loaded into a fixed bed reactor, and quartz sand is loaded at two ends of the fixed bed reactor. Introduction of synthesis gas (H)₂CO 1:1) and the starting butene oligomer (butene dimer content 98.8%, where 2,4, 4-trimethyl-1-pentene content is 89.6% and 2,4, 4-trimethyl-2-pentene content is 9.2%), which is fed into the reaction system by means of a high-pressure pump, the synthesis gas being fed directly in gaseous form. At 393K, 5MPa and the hourly space velocity of butylene oligomer liquid of 2.0h^-1The space velocity of the synthesis gas is 1000h^-1The hydroformylation reaction is carried out under the conditions. The reaction product was collected at 2.5 ℃ via a collection tank equipped with a recirculating cooler. The obtained liquid phase product is analyzed by HP-7890N gas chromatography, and N-propanol is used as an internal standard method for analysis and calculation. The reaction results are shown in Table 1.

3) Preparation of high-carbon aldehyde hydrogenation heterogeneous catalyst

373K reaction conditions, 95g of Ni (NO)₃)₂·6H₂O、12.2g Cu(NO₃)₂·3H₂O、17.8gMg(NO₃)₂·6H₂O、3.69g Co(NO₃)₂·6H₂O was dissolved in 500ml of boiling water. 373K reaction conditions, 75g Na₂CO₃Dissolved in 700ml of boiling water. Under the condition of rapid stirring, Ni (NO) is added₃)₂-Cu(NO₃)₂-Mg(NO₃)₂-Co(NO₃)₂Pouring Na into the solution according to the concentration of 100ml/min₂CO₃In solution. After the Ni-Cu-Mg-Co solution was poured in, 11.5g of the solution was quickly added and treated with ammonia (temperature 673K, ammonia gas volume space velocity 1000 h)^-1Treatment time 16h) of diatomaceous earth powder, the reaction mixture was stirred for 5 min. After filtration, the filter cake was washed with 353K hot water, the conductivity of the effluent washing water was checked, and washing was stopped when the conductivity dropped to 1800. mu.s. 323K reaction conditions, the filter cake was placed in 300ml of 0.25 wt% NaOH solution and stirred for 3 h. Then filtered, the filter cake 333K was dried for 5h, 353K for 5h and 393K for 10 h.

4) High carbon aldehyde hydrogenation reaction process

Adding the prepared high-carbon aldehyde hydrogenation heterogeneous catalyst into a trickle bed reactor, introducing hydrogen, wherein the reduction temperature of the catalyst is 698K, 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 high-carbon aldehyde is pumped into a reactor by a high-pressure metering pump to start reaction, the hydrogenation reaction temperature is 413K, the reaction pressure is 3MPa, and the liquid volume space velocity is 0.8h^-1The hydrogen/higher aldehyde molar ratio was 10. Collecting the product in a cold trap collecting tank, analyzing the liquid product by using HP-7890N gas chromatography equipped with an HP-5 capillary column and an FID detector, adopting sec-butyl alcohol as an internal standard, and analyzing the reaction tail gas on line by using HP-7890N gas chromatography equipped with a Porapak-QS column and a TCD detector. The reaction results are shown in Table 2.

Example 2

1) Hydroformylation heterogeneous catalyst preparation

The hydroformylation heterogeneous catalyst was prepared as in example 1.

2) Butene oligomer hydroformylation reaction process

The prepared hydroformylation heterogeneous catalyst is loaded into a fixed bed reactor, and quartz sand is loaded at two ends of the fixed bed reactor. Introduction of synthesis gas (H)₂CO 1:1) and the starting butene oligomer (butene dimer content 98.8%, where 2,4, 4-trimethyl-1-pentene content is 89.6% and 2,4, 4-trimethyl-2-pentene content is 9.2%), which is fed into the reaction system by means of a high-pressure pump, the synthesis gas being fed directly in gaseous form. At 373K, 3MPa and the hourly space velocity of butylene oligomer liquid of 2.0h^-1The space velocity of the synthesis gas is 1000h^-1The hydroformylation reaction is carried out under the conditions. The reaction product was collected at 2.5 ℃ via a collection tank equipped with a recirculating cooler. The obtained liquid phase product is analyzed by HP-7890N gas chromatography, and N-propanol is used as an internal standard method for analysis and calculation. The reaction results are shown in Table 1.

3) Preparation of high-carbon aldehyde hydrogenation heterogeneous catalyst

Aldehyde hydrogenation heterogeneous catalyst was prepared as in example 1.

4) High carbon aldehyde hydrogenation reaction process

The high carbon aldehyde prepared by the methodAdding hydrogenation heterogeneous catalyst into trickle bed reactor, introducing hydrogen, reducing temperature of catalyst of 698K, reducing time of 4h, reducing pressure of 0.5MPa, and reducing gas space velocity of 1000h^-1. After the catalyst is reduced by hydrogen, the raw material high-carbon aldehyde is pumped into a reactor through a high-pressure metering pump to start reaction, the hydrogenation reaction temperature is 393K, the reaction pressure is 1MPa, and the liquid volume space velocity is 0.8h^-1The hydrogen/higher aldehyde molar ratio was 10. Collecting the product in a cold trap collecting tank, analyzing the liquid product by using HP-7890N gas chromatography equipped with an HP-5 capillary column and an FID detector, adopting sec-butyl alcohol as an internal standard, and analyzing the reaction tail gas on line by using HP-7890N gas chromatography equipped with a Porapak-QS column and a TCD detector. The reaction results are shown in Table 2.

Example 3

1) Hydroformylation heterogeneous catalyst preparation

The hydroformylation heterogeneous catalyst was prepared as in example 1.

2) Butene oligomer hydroformylation reaction process

The prepared hydroformylation heterogeneous catalyst is loaded into a fixed bed reactor, and quartz sand is loaded at two ends of the fixed bed reactor. Introduction of synthesis gas (H)₂CO is 1:1 and raw material butylene oligomer (butylene trimer content is 95.2%), the butylene oligomer is conveyed into a reaction system by a high-pressure pump, and synthesis gas is directly fed in a gas form. At 403K, 7MPa and the hourly space velocity of the butylene oligomer liquid of 1.85h^-1The space velocity of the synthesis gas is 1000h^-1The hydroformylation reaction is carried out under the conditions. The reaction product was collected at 2.5 ℃ via a collection tank equipped with a recirculating cooler. The obtained liquid phase product is analyzed by HP-7890N gas chromatography, and N-propanol is used as an internal standard method for analysis and calculation. The reaction results are shown in Table 1.

3) Preparation of high-carbon aldehyde hydrogenation heterogeneous catalyst

Aldehyde hydrogenation heterogeneous catalyst was prepared as in example 1.

4) High carbon aldehyde hydrogenation reaction process

Adding the prepared high-carbon aldehyde hydrogenation heterogeneous catalyst into a trickle bed reactor, introducing hydrogen, wherein the reduction temperature of the catalyst is 698K, the reduction time is 4h, the reduction pressure is 0.5MPa, and the space velocity of the reduction gas is 1000h^-1. Catalyst hydrogen reductionThen, pumping the raw material high-carbon aldehyde into a reactor through a high-pressure metering pump to start reaction, wherein the hydrogenation reaction temperature is 423K, the reaction pressure is 5MPa, and the liquid volume space velocity is 0.8h^-1The hydrogen/higher aldehyde molar ratio was 10. Collecting the product in a cold trap collecting tank, analyzing the liquid product by using HP-7890N gas chromatography equipped with an HP-5 capillary column and an FID detector, adopting sec-butyl alcohol as an internal standard, and analyzing the reaction tail gas on line by using HP-7890N gas chromatography equipped with a Porapak-QS column and a TCD detector. The reaction results are shown in Table 2.

Example 4

1) Hydroformylation heterogeneous catalyst preparation

The hydroformylation heterogeneous catalyst was prepared as in example 1.

2) Butene oligomer hydroformylation reaction process

The prepared hydroformylation heterogeneous catalyst is loaded into a fixed bed reactor, and quartz sand is loaded at two ends of the fixed bed reactor. Introduction of synthesis gas (H)₂CO is 1:1 and raw material butylene oligomer (butylene trimer content is 95.2%), the butylene oligomer is conveyed into a reaction system by a high-pressure pump, and synthesis gas is directly fed in a gas form. At 383K, 5MPa and the hourly space velocity of the butylene oligomer liquid of 1.85h^-1The space velocity of the synthesis gas is 1000h^-1The hydroformylation reaction is carried out under the conditions. The reaction product was collected at 2.5 ℃ via a collection tank equipped with a recirculating cooler. The obtained liquid phase product is analyzed by HP-7890N gas chromatography, and N-propanol is used as an internal standard method for analysis and calculation. The reaction results are shown in Table 1.

3) Preparation of high-carbon aldehyde hydrogenation heterogeneous catalyst

Aldehyde hydrogenation heterogeneous catalyst was prepared as in example 1.

4) High carbon aldehyde hydrogenation reaction process

Adding the prepared high-carbon aldehyde hydrogenation heterogeneous catalyst into a trickle bed reactor, introducing hydrogen, wherein the reduction temperature of the catalyst is 698K, 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 high-carbon aldehyde is pumped into a reactor by a high-pressure metering pump to start reaction, the hydrogenation reaction temperature is 413K, the reaction pressure is 3MPa, and the liquid volume space velocity is 0.5h^-1The hydrogen/higher aldehyde molar ratio was 10. Product recoveryThe liquid product is collected in a cold trap collecting tank, the liquid product is analyzed by using HP-7890N gas chromatography provided with an HP-5 capillary column and an FID detector, sec-butyl alcohol is used as an internal standard, and reaction tail gas is analyzed on line by using HP-7890N gas chromatography provided with a Porapak-QS column and a TCD detector. The reaction results are shown in Table 2.

TABLE 1 results of heterogeneous hydroformylation of butene oligomers

TABLE 2 reaction results of hydrogenation of higher aldehydes to higher alcohols

From the above results, it can be seen that the method for preparing higher alcohols from butene oligomers, provided by the present invention, 1) reduces the separation cost of the catalyst, the reactants and the products due to the adoption of the novel solid heterogeneous catalyst, compared with the existing hydroformylation reaction technology applied in industry; the reaction process is simple and easy to implement, is suitable for large-scale industrial production, and has excellent reaction activity and selectivity and good reaction stability. 2) In the high-carbon aldehyde hydrogenation reaction, a novel nickel-based heterogeneous catalyst is used, the catalyst has excellent low-temperature activity and alcohol product selectivity, the subsequent purification and separation cost of the product is reduced, and the economic benefit of the reaction process for preparing high-carbon alcohol by aldehyde hydrogenation is effectively improved. The method can prepare the high-added-value chemical high-carbon alcohol from the butylene oligomer through two-step reaction of multiphase hydroformylation and aldehyde hydrogenation, and has higher economic value and wide industrial application prospect.

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.