CN114380672B - Method for preparing 1, 6-glyoxal by hydroformylation of 1, 3-butadiene - Google Patents

Method for preparing 1, 6-glyoxal by hydroformylation of 1, 3-butadiene Download PDF

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CN114380672B
CN114380672B CN202210021519.2A CN202210021519A CN114380672B CN 114380672 B CN114380672 B CN 114380672B CN 202210021519 A CN202210021519 A CN 202210021519A CN 114380672 B CN114380672 B CN 114380672B
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butadiene
water
catalyst
rhodium
synthesis gas
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CN114380672A (en
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白发红
王浩浩
陈锴
王科
王晓光
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Weifang Sanli Benno Chemical Industry Co ltd
Qingdao Sanli Bennuo New Materials Ltd By Share Ltd
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Weifang Sanli Benno Chemical Industry Co ltd
Qingdao Sanli Bennuo New Materials Ltd By Share Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
    • C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/822—Rhodium

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract

The invention discloses a method for preparing 1, 6-hexanedial by hydroformylation of 1, 3-butadiene, and belongs to the technical field of fine chemical engineering. The method comprises the following steps: mixing a catalyst, a water-soluble diphosphine ligand, a cosolvent, a polymerization inhibitor and deionized water to obtain a pre-reaction solution; mixing 1, 3-butadiene, synthesis gas and pre-reaction liquid, reacting at 50-120 deg.c and 1.0-5.0 MPa for 0.5-6 hr, and letting stand to separate phase to obtain 1, 6-hexanedialdehyde. The method provided by the invention can solve the difficult problems of difficult separation and recycling of the catalyst and the product, reduce the separation energy consumption, and simultaneously ensure that the 1, 3-butadiene has higher conversion rate and product selectivity.

Description

Method for preparing 1, 6-glyoxal by hydroformylation of 1, 3-butadiene
Technical Field
The invention relates to the technical field of fine chemical engineering, in particular to a method for preparing 1, 6-glyoxal by hydroformylation of 1, 3-butadiene.
Background
The 1, 6-hexanedial is not only a quick-acting broad-spectrum chemical sterilizing agent, but also has the characteristics of high activity, quick response, more combination, stable product, strong resistance to acid, water and enzyme, and the like, and can be used for bonding and repairing biological tissues and human organs. More importantly, the 1, 6-hexanedialdehyde can be directly used as an important organic synthesis raw material for synthesizing C6 compounds with higher application value and larger market demand, such as adipic acid (1, 6-adipic acid), hexamethylenediamine (1, 6-hexanediamine), hexanediol (1, 6-hexanediol) and the like, wherein the C6 compounds are all industrially important monomers for synthesizing polyester, polyamide (nylon 66 or nylon 610) and polyurethane.
Currently, 1, 6-hexanedial is synthesized mainly by multi-step oxidation of 1, 6-cyclohexanediol or cyclohexene. Common oxidants include nitric acid, sodium periodate, iodobenzene diacetate, hydrogen peroxide and ozone. However, these oxidation methods have problems such as difficult availability of sources of reaction raw materials and oxidizing agents, high price, difficult circulation, environmental friendliness, or low yield of target products.
The olefin hydroformylation reaction process has remarkable characteristics of strong atom economy, wide product application and the like, but until now, olefin substrates are mainly concentrated on non-conjugated ends or internal olefins in industrial production, and the hydroformylation reaction is very challenging for conjugated olefins with molecular structures, such as butadiene, mainly due to the lack of regioselectivity of the reaction and the formation of complex mixed products. Patent CN1087078 discloses a process for preparing 1, 6-hexanedial by hydroformylation of 1, 3-butadiene, but with lower selectivity. Patent CN108137451 uses phosphite ligand modified Rh to catalyze the hydroformylation of 1, 3-butadiene to make 1, 6-glyoxal with selectivity up to 50%. However, the ligand is sensitive to air and moisture, so that the ligand has the problem of poor stability. Meanwhile, after the homogeneous phase reaction is finished, the problems of separation and recycling of the catalyst and the product exist.
Disclosure of Invention
Aiming at the technical problems that the selectivity of preparing 1, 6-hexanedial by hydroformylation is low and the catalyst and the product are not easy to separate in the background technology, the invention provides a method for preparing 1, 6-hexanedial by hydroformylation of 1, 3-butadiene, which can solve the problems that the catalyst and the product are not easy to separate and recycle, reduces the separation energy consumption, and has high conversion rate of 1, 3-butadiene and high selectivity of the product.
In order to solve the technical problems, the invention provides a method for preparing 1, 6-glyoxal by hydroformylation of 1, 3-butadiene, which is characterized by comprising the following steps:
mixing a catalyst, a water-soluble diphosphine ligand, a cosolvent, a polymerization inhibitor and deionized water to obtain a pre-reaction solution;
Mixing 1, 3-butadiene, synthesis gas and pre-reaction liquid, reacting at 50-120 ℃ and 1.0-5.0 MPa for 0.5-6 h, standing for phase separation to obtain 1, 6-glyoxal;
The synthesis gas is a mixed gas of carbon monoxide and hydrogen;
the molecular formula of the water-soluble diphosphine ligand is shown as a formula B:
preferably, the catalyst is a rhodium-containing compound or rhodium-containing complex, and the molar ratio of the 1, 3-butadiene to rhodium in the catalyst is 300-5000:1.
Preferably, the rhodium-containing compound or rhodium-containing complex is RhCl3·nH2O、Rh2(CH3COO)4、Rh(acac)(CO)2、RhCl(TPPTS)3、HRh(CO)(TPPTS)3 or HRh (CO) 2 (BISBIS).
Preferably, the cosolvent is one or more solutions of polyethylene glycols, low-carbon alcohols, cyclodextrins, amides and nitriles.
Preferably, the mass ratio of the cosolvent to the 1, 3-butadiene is 1:50-1000; the volume ratio of the cosolvent to the deionized water is 8:2-2:8.
Preferably, the molar ratio of the water-soluble diphosphine ligand to rhodium in the catalyst is 2-20:1.
Preferably, the polymerization inhibitor is one or more of sodium nitrite, tert-butyl catechol, diethyl hydroxylamine and polymerization inhibitor JD-A249.
Preferably, the mass ratio of the polymerization inhibitor to the 1, 3-butadiene is 1:50-1000.
Preferably, the volume ratio of carbon monoxide to hydrogen in the synthesis gas is 1:0.7-1.5.
Preferably, the molar ratio of the 1, 3-butadiene to the synthesis gas is 1:1-1.5.
Compared with the prior art, the invention has the following technical effects:
(1) In the preparation method provided by the invention, the water-soluble diphosphine ligand has good stability and strong poisoning resistance, is not easy to oxidize and decompose, and can well stabilize the rhodium catalyst, so that the loss of the catalyst in the production process is reduced; the water-soluble diphosphine ligand and the cosolvent are matched for use, so that the reaction rate of the hydroformylation reaction is improved, and the reaction can be effectively completed at a lower temperature of 60-80 ℃, thereby reducing the self-polymerization of 1, 3-butadiene and further improving the selectivity and the yield of the reaction.
(2) The invention adopts a method for preparing 1, 6-hexanedial by water-organic heterogeneous catalysis of 1, 3-butadiene, utilizes a catalyst system formed by combining a water-soluble ligand, a rhodium compound and a cosolvent, and after the reaction is finished, water/organic two-phase natural phase separation (the upper layer is a product phase, and the lower layer is a catalyst water phase), the ligand, the rhodium catalyst and an auxiliary agent are all in the water phase, the product and the catalyst are simply separated, the palladium catalyst and the product can be completely separated without a high-temperature rectification method, the separation process is simple, and the production cost is low.
(3) The invention adopts 1, 3-butadiene as a reaction raw material, the raw material is relatively cheap and easy to obtain, and the hydroformylation reaction has the characteristic of strong atomic economy, so that the method for preparing the 1, 3-butadiene into the glyoxal through the hydroformylation reaction accords with the economic and environment-friendly process technology.
Drawings
FIG. 1 is a nuclear magnetic resonance spectrum of a water-soluble diphosphine ligand provided by the invention;
FIG. 2 is a phosphine spectrum of the water-soluble bisphosphine ligand provided by the present invention.
Detailed Description
The invention also provides a method for preparing 1, 6-glyoxal by hydroformylation of 1, 3-butadiene, which is characterized by comprising the following steps:
mixing a catalyst, a water-soluble diphosphine ligand, a cosolvent, a polymerization inhibitor and deionized water to obtain a pre-reaction solution;
Mixing 1, 3-butadiene, synthesis gas and pre-reaction liquid, reacting at 50-120 ℃ and 1.0-5.0 MPa for 0.5-6 h, standing for phase separation to obtain 1, 6-glyoxal;
The synthesis gas is a mixed gas of carbon monoxide and hydrogen;
the molecular formula of the water-soluble diphosphine ligand is shown as a formula B:
The method mixes the catalyst, the water-soluble diphosphine ligand, the cosolvent, the polymerization inhibitor and deionized water to obtain a pre-reaction solution. In the present invention, the catalyst is preferably a rhodium-containing compound or rhodium-containing complex, more preferably one or more of RhCl3·nH2O、Rh2(CH3COO)4、Rh(acac)(CO)2、RhCl(TPPTS)3、HRh(CO)(TPPTS)3 and HRh (CO) 2 (BISBIS) (wherein acac: acetylacetonate anion; BISBIS: sodium sulfonate salt of 2,2 '-bis (diphenylphosphinomethyl) -1,1' -biphenyl), most preferably HRh (CO) (TPPTS) 3. In the present invention, the concentration of rhodium in the pre-reaction liquid in the catalyst is preferably 100. Mu.g/mL-500 mg/mL.
In the invention, the cosolvent is preferably one or more solutions of polyethylene glycols, low-carbon alcohols, cyclodextrins, amides and nitriles; the polyethylene glycol compound is preferably one or more of PEG-200, PEG-400, PEG-600, PEG-800 and PEG-20000; the lower alcohols are preferably one or more of methanol, ethanol, isopropanol and butanol; the cyclodextrin is preferably one or more of alpha-cyclodextrin, beta-cyclodextrin, gamma-cyclodextrin, methylated alpha-cyclodextrin, methylated beta-cyclodextrin and methylated gamma-cyclodextrin, more preferably beta-cyclodextrin; the amide is preferably one or more of formamide, N-methylformamide and N, N-dimethylformamide, and more preferably N-methylformamide. In the invention, the mass ratio of the cosolvent to the 1, 3-butadiene is 1:50-1000; the volume ratio of the cosolvent to the deionized water is 8:2-2:8.
In the invention, the polymerization inhibitor is preferably one or more of sodium nitrite, tert-butylcatechol, diethylhydroxylamine and polymerization inhibitor JD-A249. In the invention, the mass ratio of the polymerization inhibitor to the 1, 3-butadiene is 1:50-1000.
In the present invention, the molar ratio of the water-soluble bisphosphine ligand to rhodium in the catalyst is preferably 2 to 20:1. In the invention, the water-soluble diphosphine ligand is prepared by sulfonating a compound A. The specific operation is as follows: under nitrogen atmosphere, 0.5g of compound A and 2ml of concentrated sulfuric acid are mixed and stirred for dissolution, cooled to 0-6 ℃, then 6ml of 50% fuming sulfuric acid is added dropwise, after the dropwise addition is completed, the temperature is raised to 20-30 ℃ after the stirring reaction is carried out for 48 hours at 0 ℃, 100ml of ice water is added for cooling, the PH of the solution is neutralized to 7-9 by 30% sodium hydroxide 1N, and then the concentrate is obtained by concentration. Mixing the concentrate with ethanol, filtering to remove sodium sulfate, and drying to obtain water-soluble diphosphine ligand. The structural formula of the compound A is as follows:
in the present invention, the compound a is prepared by the method provided in patent CN102010442 a.
The invention mixes 1, 3-butadiene, synthesis gas and pre-reaction liquid, reacts for 0.5 to 6 hours at 50 to 120 ℃ and 1.0 to 5.0MPa, stands still and phase separates to obtain 1, 6-hexanedialdehyde. In the present invention, the molar ratio of the 1, 3-butadiene to rhodium in the catalyst is preferably 300 to 5000:1. In the invention, when the cosolvent is liquid, the volume ratio of the cosolvent to the deionized water is 8:2-2:8; when the cosolvent is solid, the mass ratio of the cosolvent to the 1, 3-butadiene is 1:50-1000. In the invention, the mass ratio of the 1, 3-butadiene to the polymerization inhibitor is 50-1000: 1.
In the invention, the synthesis gas is a mixed gas of carbon monoxide and hydrogen, and the volume ratio of the carbon monoxide to the hydrogen is preferably 1:0.7-1.5. In the present invention, the molar ratio of 1, 3-butadiene to synthesis gas is preferably 1:1 to 1.5.
According to the invention, the preparation of 1, 6-hexanedial by hydroformylation of 1, 3-butadiene can be realized in a water-organic heterogeneous catalytic system, the preparation is determined by the interaction among water, a cosolvent, a water-soluble phosphine ligand and olefin, and from the aspects of the structural characteristics of the ligand and water, the sulfonate-type anionic water-soluble phosphine ligand has stronger solubility and affinity in water, so that the effective immobilization of rhodium-ligand is ensured, the loss of catalyst in the reaction is reduced, and the ligand has good stability and strong poisoning resistance and is not easy to oxidize and decompose. Secondly, the aqueous phase catalyst and the reaction product form a liquid/liquid two-phase system, the aqueous phase containing the catalyst and the product aldehyde phase can be separated through simple phase separation, and new butadiene raw materials can be added for the next catalytic cycle; third, compared with homogeneous phase reaction, mass transfer is limited in two-phase catalytic reaction, but the addition of cosolvent can effectively improve mass transfer between aqueous phase catalyst and organic raw material phase, and improve catalytic activity.
In the present invention, the hydroformylation reaction is preferably carried out in a stainless steel autoclave, and the air in the autoclave is replaced with synthesis gas 3 or more times so as to sufficiently remove the air. The phase separation is preferably carried out in a phase separator, the upper layer is an oil phase crude product after the phase separation is finished, the lower layer is a catalyst aqueous solution, and the catalyst aqueous solution can be returned to the reaction kettle for continuous recycling.
The technical solutions provided by the present invention are described in detail below in conjunction with examples for further illustrating the present invention, but they should not be construed as limiting the scope of the present invention.
Example 1
59Mg HRh (CO) (TPPTS) 3, 96mg of water-soluble diphosphine ligand, 46.5mg of methylated beta-cyclodextrin, 46.5mg of sodium nitrite, 3mL of methanol, 6mL of formamide and 1.5mL of deionized water are sequentially added into a 50mL stainless steel high-pressure reaction kettle, the reaction kettle is screwed up, then the air in the reaction kettle is replaced by synthesis gas (the volume ratio of hydrogen to carbon monoxide is 1:1.2) for more than 4 times, and the pressure of the reaction kettle is filled with the synthesis gas to 0.5MPa. Connecting the reaction kettle with a1, 3-butadiene storage tank, opening a metering pump, feeding at a feeding speed of 1.0mL/min, opening a feeding port of the reaction kettle to start timing feeding when the current pressure of the metering pump is 0.5MPa, timing for 1.5min, adding 1, 3-butadiene 1.5mL, stopping feeding, connecting the reaction kettle with a synthesis gas, supplementing synthesis gas to the pressure of the reaction kettle of 2.5MPa, reacting at 60 ℃ for 5 hours (the pressure of the reaction kettle is concerned at the moment in the middle process and is timely supplemented when the pressure is less than 2.5 MPa), cooling to room temperature after the reaction is finished, opening the reaction kettle by venting the synthesis gas, taking an organic phase for gas chromatography analysis, wherein the conversion rate of 1, 3-butadiene is 96%, and the selectivity of 1, 6-glyoxal is 45%. The main byproducts are 18% of n-valeraldehyde, 14% of isopentenyl aldehyde, 7% of 2-pentenal, 8% of 4-pentenal, 5% of butadiene dimer 4-vinyl-1-cyclohexene and its hydroformylation product, and the polymer with carbon content greater than 12 contains only 3%.
Example 2
The reaction conditions and the operation method were the same as in example 1 except that the catalyst was the lower catalyst separated after the end of the reaction of example 1, i.e., the lower catalyst phase was charged into the reaction vessel after the end of the reaction of example 1 and 1, 3-butadiene was added to react, and the operation was circulated three times while sampling the upper oil phase after each end of the reaction, respectively, and the change in rhodium content in the oil phase was detected by ICP-MS. The specific results are shown in Table 1.
TABLE 1 variation of rhodium content
As can be seen from table 1, three consecutive cycles, the catalyst content detected in the oil phase was close and lower, indicating that: the method provided by the invention can effectively reduce the loss of the catalyst in the reaction.
Example 3
45Mg HRh (CO) (TPPTS) 3 of water-soluble bisphosphine ligand 110mg,62mg of tertiary butyl catechol, 2mL of acetonitrile, 4mL of PEG-200,3mL of methanol and 1mL of deionized water are sequentially added into a 50mL stainless steel high-pressure reaction kettle, the air in the reaction kettle is replaced by synthesis gas for more than 4 times after the reaction kettle is screwed up, the reaction kettle pressure is filled with the synthesis gas to 0.5MPa (the volume ratio of hydrogen to carbon monoxide is 1:1.2), the reaction kettle is connected with a1, 3-butadiene storage tank, a metering pump is opened, feeding is started according to the feeding speed of 1.0mL/min, when the current pressure of the metering pump is 0.5MPa, a feeding port of the reaction kettle is opened for timing feeding for 2.0min, 2.0mL of 1, 3-butadiene is added, feeding is stopped, the reaction kettle is connected with synthesis gas, the synthesis gas is supplemented to the reaction kettle pressure of 2.0MPa, the reaction kettle is timely supplemented at 70 ℃ for 5 hours (the reaction kettle pressure is timely supplemented when the reaction kettle pressure is less than 2.0MPa in the middle process), the reaction kettle is cooled to room temperature after the reaction is completed, the reaction kettle is opened, the 1.1% of 1, 1% of the 1-3-1% of the dialdehyde is obtained by taking the 1, and the 1% of the 1-3% of the 1% of the dialdehyde has been analyzed by the phase, and the selectivity is obtained by taking the 1% of the phase has been 1 phase has been analyzed. The byproducts mainly comprise 9% of n-valeraldehyde, 17% of isopentenyl aldehyde, 10% of 2-pentenal and 4-pentenal, 7% of butadiene dimer 4-vinyl-1-cyclohexene and hydroformylation products thereof, and 5% of polymer containing carbon more than 12.
Comparative example 1
The procedure is the same as in example 1, except that no cosolvent is added, and the specific procedure is as follows:
59mg HRh (CO) (TPPTS) 3 mg of water-soluble diphosphine ligand 96mg,46.5mg of sodium nitrite and 10.5mL of deionized water are sequentially added into a 50mL stainless steel high-pressure reaction kettle, the reaction kettle is screwed up, then the air in the reaction kettle is replaced by synthetic gas (the volume ratio of hydrogen to carbon monoxide is 1:1.2) for more than 4 times, and the pressure of the reaction kettle is filled with the synthetic gas to 0.5MPa. Connecting the reaction kettle with a 1, 3-butadiene storage tank, opening a metering pump, feeding at a feeding speed of 1.0mL/min, opening a feeding port of the reaction kettle to start timing feeding when the current pressure of the metering pump is 0.5MPa, timing for 1.5min, adding 1, 3-butadiene 1.5mL, stopping feeding, connecting the reaction kettle with a synthesis gas, supplementing synthesis gas to the pressure of the reaction kettle of 2.5MPa, reacting at 60 ℃ for 5 hours (the pressure of the reaction kettle is concerned at the moment in the middle process and is timely supplemented when the pressure is less than 2.5 MPa), cooling to room temperature after the reaction is finished, opening the reaction kettle by venting the synthesis gas, taking an organic phase for gas chromatography analysis, wherein the conversion rate of 1, 3-butadiene is 80%, and the selectivity of 1, 6-glyoxal is less than 3%. The product contains 20% of n-valeraldehyde and isopentenyl aldehyde, 5% of butadiene dimer and 5% of hydroformylation product, and 45% of polymer with carbon number more than 12.
Comparative example 2
The procedure was the same as in example 1, except that no polymerization inhibitor was added, and the specific procedure was as follows:
59mg HRh (CO) (TPPTS) 3, 96mg of water-soluble diphosphine ligand, 46.5mg of methylated beta-cyclodextrin and 1.5mL of deionized water are sequentially added into a 50mL stainless steel high-pressure reaction kettle, the air in the reaction kettle is replaced by synthesis gas (the volume ratio of hydrogen to carbon monoxide is 1:1.2) for more than 4 times after the reaction kettle is screwed, and the pressure of the reaction kettle is filled with the synthesis gas to 0.5MPa. Connecting the reaction kettle with a1, 3-butadiene storage tank, opening a metering pump, feeding at a feeding speed of 1.0mL/min, opening a feeding port of the reaction kettle to start timing feeding when the current pressure of the metering pump is 0.5MPa, timing for 1.5min, adding 1, 3-butadiene 1.5mL, stopping feeding, connecting the reaction kettle with a synthesis gas, supplementing synthesis gas to the pressure of the reaction kettle to be 2.5MPa, reacting at 60 ℃ for 5 hours (the pressure of the reaction kettle is concerned at the moment in the middle process and is timely supplemented when the pressure is less than 2.5 MPa), cooling to room temperature after the reaction is finished, opening the reaction kettle by venting the synthesis gas, taking an organic phase for gas chromatography analysis, wherein the conversion rate of 1, 3-butadiene is 94%, and the selectivity of 1, 6-glyoxal is 37%. Butadiene dimer 4-vinyl-1-cyclohexene and its hydroformylation product 10%, and the polymer containing carbon content more than 12% is 12%.
Comparative example 3
The procedure is as in example 1, except that no water-soluble phosphine ligand is added, and the specific procedure is as follows:
59mg HRh (CO) (TPPTS) 3 mg methylated beta-cyclodextrin, 46.5mg sodium nitrite, 3mL methanol, 6mL formamide and 1.5mL deionized water are sequentially added into a 50mL stainless steel high-pressure reaction kettle, the air in the reaction kettle is replaced by synthesis gas (the volume ratio of hydrogen to carbon monoxide is 1:1.2) for more than 4 times after the reaction kettle is screwed, and the pressure of the reaction kettle is filled with the synthesis gas to 0.5MPa. Connecting the reaction kettle with a1, 3-butadiene storage tank, opening a metering pump, feeding at a feeding speed of 1.0mL/min, opening a feeding port of the reaction kettle to start timing feeding when the current pressure of the metering pump is 0.5MPa, timing for 1.5min, adding 1, 3-butadiene 1.5mL, stopping feeding, connecting the reaction kettle with a synthesis gas, supplementing synthesis gas to the pressure of the reaction kettle to be 2.5MPa, reacting at 60 ℃ for 5 hours (the pressure of the reaction kettle is concerned at the moment in the middle process and is timely supplemented when the pressure is less than 2.5 MPa), cooling to room temperature after the reaction is finished, opening the reaction kettle by venting the synthesis gas, taking an organic phase for gas chromatography analysis, wherein the conversion rate of 1, 3-butadiene is 53%, and the selectivity of 1, 6-glyoxal is 0%. The major by-products are 37% n-valeraldehyde and isopentenyl aldehyde, 40% butadiene dimer 4-vinyl-1-cyclohexene and its hydroformylation products, and 23% of the polymer having a carbon content greater than 12% of 12%.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.

Claims (8)

1. A method for preparing 1, 6-glyoxal by hydroformylation of 1, 3-butadiene, which is characterized by comprising the following steps:
mixing a catalyst, a water-soluble diphosphine ligand, a cosolvent, a polymerization inhibitor and deionized water to obtain a pre-reaction solution;
mixing 1, 3-butadiene, synthesis gas and a pre-reaction liquid, reacting for 0.5-6 hours at 50-120 ℃ and 1.0-5.0 MPa, standing and phase-separating to obtain 1, 6-glyoxal;
The synthesis gas is a mixed gas of carbon monoxide and hydrogen;
the catalyst is a rhodium-containing compound or rhodium-containing complex, and the molar ratio of the 1, 3-butadiene to rhodium in the catalyst is 300-5000:1;
the cosolvent is one or more solutions of methylated beta-cyclodextrin, methanol, formamide, acetonitrile and PEG-200;
The water-soluble diphosphine ligand is prepared by sulfonating a compound A, and comprises the following specific operations: mixing 0.5g of compound A with 2ml of concentrated sulfuric acid under nitrogen atmosphere, stirring and dissolving, cooling to 0-6 ℃, then dropwise adding 6ml of 50% fuming sulfuric acid, keeping the temperature of 0 ℃ after the dropwise adding is completed, stirring and reacting for 48 hours, heating to 20-30 ℃, stirring, adding 100ml of ice water for cooling, neutralizing the PH of the solution to 7-9 with 30% sodium hydroxide, and concentrating to obtain a concentrate; mixing the concentrate with ethanol, filtering to remove sodium sulfate, and drying to obtain water-soluble diphosphine ligand; the structural formula of the compound A is as follows:
。
2. The method of claim 1, wherein the rhodium-containing compound or rhodium-containing complex is RhCl3•nH2O、Rh2(CH3COO)4、Rh(acac)(CO)2、RhCl(TPPTS)3、HRh(CO)(TPPTS)3 or HRh (CO) 2 (BISBIS).
3. The method according to claim 1, wherein the mass ratio of the cosolvent to the 1, 3-butadiene is 1:50-1000; the volume ratio of the cosolvent to the deionized water is 8:2-2:8.
4. The method of claim 1, wherein the molar ratio of the water-soluble bisphosphine ligand to rhodium in the catalyst is 2 to 20:1.
5. The method according to claim 1, wherein the polymerization inhibitor is one or more of sodium nitrite, tert-butylcatechol, diethylhydroxylamine and polymerization inhibitor JD-A249.
6. The method according to claim 1, wherein the mass ratio of the polymerization inhibitor to 1, 3-butadiene is 1:50-1000.
7. The method of claim 1, wherein the volume ratio of carbon monoxide to hydrogen in the synthesis gas is 1:0.7-1.5.
8. The method of claim 1, wherein the molar ratio of 1, 3-butadiene to synthesis gas is 1:1 to 1.5.
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