Gas chromatography analysis equipment and gas chromatography analysis method for mixed butene hydroformylation reaction products

Abstract

The invention relates to the field of chemical analysis, and discloses a gas chromatography analysis device and an analysis method for a mixed butene hydroformylation reaction product. The device comprises a chromatographic column and a detector. The device comprises n chromatographic columns connected in series, wherein chromatographic columns 2 to n are respectively provided with an injection valve, and the injection valve can seal a gas component that first passes through the injection valve in a chromatographic column provided with the injection valve and allow a gas component that later passes through the injection valve to enter a next chromatographic column, and each chromatographic column is separately connected to the detector, wherein n is a natural number ≥2. The device is used to analyze a mixed butene hydroformylation reaction product, and simultaneously takes into account various components of a liquid phase and a gas phase in the reaction product, accurately reflects changes in various components in a hydroformylation reaction process, and has the advantages of simple operation, fast analysis speed, and accurate results.

Description

Technical Field

[0001] The present invention relates to the field of organic and inorganic analysis, and in particular to a gas chromatography analysis device and a gas chromatography analysis method for mixed butene hydroformylation reaction products. Background Art

[0002] The hydroformylation of olefins is of great industrial significance. Currently, dozens of industrial production facilities are in operation worldwide, producing millions of tons of various products annually. Aldehydes and their derivatives derived from low-carbon olefins account for the vast majority of this production. While significant attention is paid to production technology, analytical methods are often employed to obtain qualified products and detect intermediates.

[0003] Currently, most industrial processes for producing aldehydes from light olefins utilize low-pressure rhodium-based catalysts. Continuous industrial production involves directly introducing the raw materials H2 / CO and olefins into a catalyst solution. Conditions must be controlled to ensure that the hydroformylation reaction occurs in the main liquid phase. After the reaction, separation is performed. Unreacted raw materials and catalyst solution are typically recycled back to the reactor, while the product is fed to a subsequent separation unit. During this process, intermediate products must be monitored to adjust reaction conditions over time to ensure high conversion and selectivity. The final product content after separation also needs to be determined to ultimately meet market and customer needs.

[0004] As is known to all, the hydroformylation reaction is carried out in the liquid phase, while the raw materials CO, H2 and low-carbon olefins are contacted and reacted in the catalyst solution. The concentration of different raw materials has different effects on the reaction results, and the composition of the effective ingredients needs to be determined accordingly. The product flow after the reaction includes the product aldehyde, the alkane after the side reaction hydrogenation, the dissolved unreacted mixed olefin raw material and the synthesis gas (a mixture of H2 and CO) raw material.

[0005] In the prior art, the analysis of low-pressure hydroformylation reaction raw materials and products can be divided into two categories: one is the detection of a single raw material mixed with butene and synthesis gas, and the other is the detection of intermediate products and hydroformylation products containing product aldehydes, a raw material mixed with butene and synthesis gas. Synthesis gas is detected by a TCD detector, and olefins and aldehydes are detected by an FID detector. In the prior art, multiple injections are usually used to detect synthesis gas, synthesis gas and olefins, and olefins and aldehydes respectively. For example:

[0006] Yao Cailan, Chen Gexin, et al.'s "Analysis Method for Butene Carbonylation Reaction Products" discloses an analysis of the products after the butene hydroformylation reaction. The materials include unreacted butene and its isomers, butane byproduct, and n-isovaleraldehyde. The analysis of the liquid phase products after the carbonylation reaction was performed using a Hewlett-Packard HP-5890 chromatograph with an FID detector and a 50m x 0.2mm x 0.5μm SE.30 capillary column, using hexane as the internal standard for quantification. Using a single chromatographic column for liquid phase analysis, the method effectively separates the mixed butene isomers, butane, n-isobutyraldehyde, and toluene, with relative deviations between the components ranging from 0.25 to 2.24%. However, a small amount of the synthesis gas, the other raw material, is dissolved in the reaction liquid and cannot be effectively detected and quantified using this method. In other words, the analytical method disclosed in the document does not truly reflect the composition of the reaction products.

[0007] Yao Cailan, Chen Gexin, et al.'s "Analysis Method for Butene Carbonyl Synthesis Reaction Tail Gas" discloses a method for analyzing the tail gas of a mixed butene carbonyl synthesis reaction. The tail gas after the reaction contains by-product butane, butene isomerization products, unreacted butene, synthesis gas, and a small amount of product aldehydes. The document uses a Tianmei 7890 gas chromatograph with FID and TCD detectors, a 40m*0.3mm Al2O3 capillary column for the analysis of olefins and alkanes, and a 2m*2mm TDX-01 stainless steel packed column for the analysis of synthesis gas. Using methane as the standard substance, each component was quantified using the external standard method, with a maximum relative deviation of 7.3%. A disadvantage of this method is that it does not analyze and detect small amounts of aldehydes, and therefore does not accurately reflect the true composition of the tail gas.

[0008] Ge Yujin's "Analysis of Carbonyl Synthesis Reaction Gas by Multidimensional Gas Chromatography" discloses an analysis method for analyzing reaction gas by multidimensional gas chromatography. Using an Agilent 6890 gas chromatograph, valve switching and column backflushing technology, dual TCD detectors in parallel, 4 pneumatic valves, 2 20% dicyandiamide in Chromosorb Paw, 13X molecular sieve, porapak Q, 13A molecular sieve multiple chromatographic columns, rapid separation of H2, N2, Ar, CO, CO2, C1-C3 and butyraldehyde components in carbonyl synthesis reaction gas is achieved, and external standard method is used for quantification. The detection limit of each channel is less than 0.01%, and the maximum relative deviation is 2%. This method obviously provides an analysis method for reaction gas in propylene carbonyl synthesis to produce butyraldehyde. The disadvantage of this method is that it does not involve the detection content of liquid phase products and cannot accurately reflect the composition of carbonyl synthesis reaction products.

[0009] The above literature focuses on the analysis methods of the reaction gas, reaction exhaust gas, and reaction liquid phase logistics involved in the carbonyl synthesis reaction process. However, in these methods, each reaction medium is analyzed on the same chromatograph, and the various components of the reaction liquid phase and the reaction gas phase cannot be taken into account at the same time, and the changes of the various components during the carbonyl synthesis reaction cannot be truly reflected.

[0010] However, in a continuous oxo reaction, the composition of the streams must be analyzed to facilitate adjustments to process conditions in the reaction and separation stages, thereby improving reactant conversion and product yield. Intermediate streams of oxo reaction products, particularly liquid streams, are complex, containing not only permanent gases such as H₂, CO, N₂, and O₂, but also olefins and their isomers, alkanes, and the reaction product n-isomer aldehydes. Therefore, the ability to monitor both gaseous and liquid products within the same instrument is crucial. Summary of the Invention

[0011] The present invention aims to overcome the problem in the prior art that the same gas chromatography equipment cannot simultaneously take into account the various components of the liquid phase and the gas phase in the reaction product. The present invention provides a gas chromatography analysis device and a gas chromatography analysis method for mixed butene hydroformylation reaction products. The method can simultaneously take into account the various components of the liquid phase and the gas phase in the reaction product in the same gas chromatography equipment, accurately reflect the changes in the composition of the reaction product during the hydroformylation reaction, and has the advantages of simple operation, fast analysis speed, and accurate results.

[0012] In order to achieve the above-mentioned object, the present invention provides, on one hand, a gas chromatography analysis device for mixed butene hydroformylation reaction products, the gas chromatography analysis device comprising a chromatographic column and a detector, the device comprising n chromatographic columns connected in series, chromatographic columns 2 to chromatographic columns n each being equipped with an injection valve, and the injection valve being capable of sealing the gas components that first pass through the injection valve in the chromatographic column equipped with the injection valve and allowing the gas components that later pass through the injection valve to enter the next chromatographic column, each chromatographic column being individually connected to the detector, wherein n is a natural number ≥2.

[0013] A second aspect of the present invention provides a gas chromatography analysis method for a mixed butene hydroformylation reaction product. The gas chromatography analysis method comprises: detecting and analyzing the mixed butene hydroformylation reaction product using the gas chromatography analysis equipment described in the first aspect; wherein a carrier gas carries the mixed butene hydroformylation reaction product into a chromatographic column 1 for separation, and n-1 groups of gas components among the obtained gas components are sequentially adsorbed in chromatographic columns 2 to chromatographic columns n according to the time sequence of leaving the chromatographic column 1 and sealed, and then the injection valves configured for each chromatographic column are adjusted respectively to allow the obtained gas components to enter a detector for detection.

[0014] By adopting the technical solution of the present invention, the compositions of the liquid phase and the gas phase in the reaction product can be simultaneously taken into account in the same gas chromatography equipment, the operation is simple, the analysis speed is fast, the results are accurate, and the changes in the composition of the reaction product during the hydroformylation reaction are accurately reflected. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] Figure 1 Schematic diagram of gas chromatography analysis equipment for mixed butene hydroformylation reaction products of the present invention;

[0016] Figure 2 Schematic diagram of gas chromatography analysis equipment for the mixed butene hydroformylation reaction products of Example 1-1 and Example 1-2 of the present invention;

[0017] Figure 3 This is a chromatogram of the components in the gas phase of the mixed butene hydroformylation reaction product of Example 1-1 of the present invention;

[0018] Figure 4 This is a chromatogram of the components in the liquid phase of the mixed butene hydroformylation reaction product of Example 1-2 of the present invention.

[0019] Description of Reference Numerals

[0020] 1. Chromatographic column 1 2. Chromatographic column 2 3. Chromatographic column 3

[0021] 4. TCD detector 5. FID detector 6. Liquid phase injection port DETAILED DESCRIPTION

[0022] The endpoints of the ranges and any values ​​disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoints of each range, the endpoints of each range and individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered to be specifically disclosed herein.

[0023] The inventors of the present invention have discovered through research that, in a gas chromatography analysis device, at least two chromatographic columns are connected in series, and each of the chromatographic columns in series is equipped with an injection valve. The injection valve can seal the gas components that first pass through the injection valve in the chromatographic column equipped with the injection valve and allow the gas components that pass through the injection valve later to enter the next chromatographic column. Each chromatographic column is separately connected to a detector to form a single path. Without changing the configuration of the gas chromatography analysis device, the liquid phase and the gas phase in the mixed butene hydroformylation reaction product can be taken into account simultaneously. The operation is simple and the analysis results are accurate.

[0024] It is understood that when gas chromatography is used for analysis, the content of each component in the mixed butene hydroformylation reaction product can be analyzed using a normalization method commonly used in the art. The normalization method refers to the ratio of the peak area of ​​each component in the chromatogram to the sum of the peak areas of each component in the chromatogram. For example, if detector 1 respectively obtains the peak areas of components A and B, and detector 2 respectively obtains the peak areas of components C and D, then the peak area percentage of component A is calculated as the peak area of ​​A / (the sum of the peak areas of A, B, C, and D. The peak area percentages of the remaining components are calculated similarly). During the mixed butene hydroformylation reaction, changes in the composition of the mixed butene hydroformylation reaction product and the peak area percentages of each component can be used to reflect changes in the mixed butene hydroformylation reaction.

[0025] In a first aspect, the present invention provides a gas chromatography analysis apparatus for mixed butene hydroformylation reaction products, such as Figure 1 As shown, the gas chromatography analysis equipment includes a chromatographic column and a detector. The equipment includes n chromatographic columns connected in series. Chromatographic columns 2 to chromatographic columns n are each equipped with an injection valve, and the injection valve can seal the gas components that first pass through the injection valve in the chromatographic column equipped with the injection valve and allow the gas components that pass through the injection valve later to enter the next chromatographic column. Each chromatographic column is separately connected to the detector, wherein n is a natural number ≥2.

[0026] In the present invention, the mixed butene hydroformylation reaction product refers to a mixture after the mixed butene hydroformylation reaction, including reaction product components and unreacted components.

[0027] In the present invention, preferably, chromatographic column 1 (i.e., the first chromatographic column through which the sample flows) is further configured with a first injection valve, which is used to inject the gaseous phase mixed with the butene hydroformylation reaction product. It is understood that the first injection valve also includes a carrier gas inlet and a quantitative tube.

[0028] In the present invention, preferably, the device further comprises a liquid phase inlet and a vaporization chamber, the liquid phase inlet is sequentially connected in series with the vaporization chamber and the chromatographic column 1, and the vaporization chamber is used to vaporize the liquid phase entering from the liquid phase inlet.

[0029] It will be appreciated that the mixed butene hydroformylation reaction product is a mixture of gas and liquid phases. Therefore, if a sample is taken from the gas phase of the mixed butene hydroformylation reaction product, the gas phase sample may be mixed with one or more components in the liquid phase. Similarly, if a sample is taken from the liquid phase of the mixed butene hydroformylation reaction product, the liquid phase sample may be mixed with one or more components in the gas phase. In the present invention, correction factors for each component in the mixed butene hydroformylation reaction product can also be measured according to conventional methods in the art. The specific weight content of each component can be calculated based on the obtained correction factors and the peak area percentage of each component. Details are not further described here.

[0030] In the present invention, preferably, n = 3 to 5. This preferred embodiment not only simplifies the operation of analyzing the mixed butene hydroformylation reaction product by gas chromatography, but also further improves the accuracy of the analysis results.

[0031] In the present invention, in order to simplify the operation of gas chromatography analysis of mixed butene hydroformylation reaction products and further improve the accuracy of the analysis results, preferably, the chromatographic column 1 can separate the mixed butene hydroformylation reaction products into n groups or n-1 groups of gas components, where n=3-5.

[0032] In the present invention, the mixed butene hydroformylation reaction product is a mixture of multiple components. Rationally grouping the components in the mixed butene hydroformylation reaction product and sealing each group in a different chromatographic column can further improve the accuracy of the analysis result.

[0033] In the present invention, in order to further improve the accuracy of the analysis results, preferably, the stationary phase of the chromatographic column 1 is a non-polar substance or a low-polarity substance, more preferably a polysiloxane, further preferably selected from 5% phenyl-95% methylpolysiloxane, 5% phenyl-95% dimethylpolysiloxane, 5% diphenyl-95% dimethylpolysiloxane, polydimethylsiloxane, 5% diphenyl-1% vinyl-94% dimethylpolysiloxane or poly(dimethylsiloxane)poly(1,4-bis[dimethylsiloxy]arylene)siloxane; more preferably selected from 5% phenyl-95% methylpolysiloxane or poly(dimethylsiloxane)poly(1,4-bis[dimethylsiloxy]arylene)siloxane. It will be understood that the polarity of the low-polarity substance described in the present invention is a relative value, that is, it refers to a polar substance with relatively low polarity among polar substances. For example, the low-polarity substance in the present invention refers to a polar substance having a polarity lower than that of potassium chloride deactivated alumina, sodium sulfate deactivated alumina, alumina and bonded divinylbenzene / ethylene glycol dimethacrylate.

[0034] It is understood that the "%" in the stationary phase of the present invention refers to the quantitative percentage or molar percentage of the substituents. For example, 5% phenyl-95% dimethyl polysiloxane means that the quantitative percentage or molar percentage of the phenyl substituents in the total substituents is 5%, and the quantitative percentage or molar percentage of the methyl substituents is 95%; wherein dimethyl means that one silicon atom contains two methyl substituents.

[0035] The chromatographic column 1 in the present invention is commercially available. In order to further improve the accuracy of the analysis results, preferably, the chromatographic column 1 can be commercially purchased from a chromatographic column with a brand name of BP-1, HP-1, RTX-1, DB-1, ZB-1, SE-30, DB-5, HP-5, Ultra-2, CP-Sil8CB, SPB-5, BP-5, SE-54, ZB-5, RTX-5, OV-5, MPS-5, XTI-5, PET-5, AT-5 or MDN-5.

[0036] In the present invention, in order to further improve the accuracy of the analysis results, preferably, the length of the chromatographic column 1 is 30-60 m, the inner diameter is 0.25-0.53 mm, and the film thickness is 0.5-5 μm.

[0037] In the present invention, in order to further improve the accuracy of the analysis results, preferably, the stationary phase of the chromatographic column 2 is a molecular sieve or a filler having the same separation effect, preferably selected from 5A molecular sieve, carbon molecular sieve, activated carbon, divinylbenzene nitrogen-containing heterocyclic monomer copolymer or polystyrene divinylbenzene (i.e., styrene-divinylbenzene copolymer), more preferably 5A molecular sieve.

[0038] The chromatographic column 2 in the present invention is commercially available. In order to further improve the accuracy of the analysis results, preferably, the chromatographic column 2 can be commercially purchased from a chromatographic column with the brand name HP-Molesieve, CP Molesieve, GS Molesieve, RT-Molesieve13X or MolSieve 5A; more preferably, it is a chromatographic column with the brand name HP-Molesieve.

[0039] In the present invention, in order to further improve the accuracy of the analysis results, preferably, the length of the chromatographic column 2 is 30-60 m, the inner diameter is 0.25-0.53 mm, and the film thickness is 10-50 μm.

[0040] In the present invention, in order to further improve the accuracy of the analysis results, preferably, the stationary phase of the chromatographic column 3 to the chromatographic column n is each independently a polar substance, more preferably selected from at least one of potassium chloride deactivated alumina, sodium sulfate deactivated alumina, alumina, dimethylpolysiloxane and bonded divinylbenzene / ethylene glycol dimethacrylate, and further preferably sodium sulfate deactivated alumina.

[0041] The chromatographic columns 3 to chromatographic columns n in the present invention are commercially available. In order to further improve the accuracy of the analysis results, preferably, the chromatographic columns 3 to chromatographic columns can be independently purchased from chromatographic columns with the brand names HP-Al / S, GC-Al2O3, CP-Alumina, HP-PLOT Al2O3M, GC-Alumina KCl or GsBP-PLOT Al2O3 "S", AluminaPlot, RT-Alumina; more preferably, the chromatographic column with the brand name HP-Al / S.

[0042] In the present invention, preferably, the lengths of the chromatographic columns 3 to n are independently 30-60 m, the inner diameters are 0.25-0.53 mm, and the film thicknesses are 0.10-15 μm.

[0043] In a particularly preferred embodiment of the present invention, n=3, the stationary phase of the chromatographic column 1 is poly(dimethylsiloxane)poly(1,4-bis[dimethylsiloxy]arylene)siloxane, the length of the chromatographic column 1 is 30-60m, the inner diameter is 0.25-0.53mm, and the film thickness is 0.5-5μm; preferably, the stationary phase of the chromatographic column 2 is 5A molecular sieve, the length of the chromatographic column 2 is 30-60m, the inner diameter is 0.25-0.53mm, and the film thickness is 10-50μm; preferably, the stationary phase of the chromatographic column 3 is sodium sulfate deactivated alumina, the length of the chromatographic column 3 is 30-60m, the inner diameter is 0.25-0.53mm, and the film thickness is 0.10-15μm.

[0044] In the present invention, there is no particular limitation on the type of the injection valve. The injection valve is a six-way valve or a ten-way valve, preferably a six-way valve.

[0045] In the present invention, there is no particular limitation on the type of the detector. Preferably, the detector includes a TCD detector and a FID detector. More preferably, connecting the TCD detector and the FID detector in series can further improve the accuracy of the analysis result and is simple to operate.

[0046] In a second aspect, the present invention provides a gas chromatography analysis method for a mixed butene hydroformylation reaction product, the gas chromatography analysis method comprising: detecting and analyzing the mixed butene hydroformylation reaction product using the gas chromatography analysis equipment described in the first aspect; wherein, a carrier gas carries the mixed butene hydroformylation reaction product into a chromatographic column 1 for separation, and n-1 groups of gas components among the obtained gas components are sequentially adsorbed in chromatographic columns 2 to chromatographic column n according to the order of time of leaving the chromatographic column 1 and are sealed, and then the injection valves configured for each chromatographic column are adjusted respectively so that the obtained gas components enter the detector for detection respectively.

[0047] In the present invention, preferably, the chromatographic column 1 separates the mixed butene hydroformylation reaction products, and all the obtained gas components are adsorbed in the chromatographic column 2-n and sealed. Specifically, the chromatographic column 1 separates the mixed butene hydroformylation reaction products into n groups of gas components, and each group of gas components is sequentially adsorbed on the chromatographic column 2 to the chromatographic column n and sealed. Then, the injection valves configured in each of the chromatographic columns 2-n are adjusted respectively to allow the sealed gas components to enter the detector for detection.

[0048] In a particularly preferred embodiment of the present invention, the chromatographic column 1 separates the mixed butene hydroformylation reaction product into n groups of gas components, and the n-1 group of gas components that first flow out from the chromatographic column 1 are sequentially adsorbed on the chromatographic column 2 until they are sealed in the chromatographic column n. Then, the injection valves configured in the chromatographic columns 2-n are adjusted respectively so that the sealed gas components and the components that last flow out from the chromatographic column 1 enter the detector for detection.

[0049] In the present invention, the method is particularly suitable for analyzing mixed butene hydroformylation reaction products. Preferably, the molecular weight of the components of the mixed butene hydroformylation reaction products is in the range of 2-120.

[0050] More preferably, the mixed butene hydroformylation reaction product contains at least one of methane, isovaleraldehyde, n-valeraldehyde, hydrogen, nitrogen, carbon monoxide, cyclopropane, isobutane, n-butane, trans-2-butene, 1-butene, isobutene and cis-2-butene.

[0051] Further preferably, the mixed butene hydroformylation reaction product comprises methane at a content of 0-15% by weight, isovaleraldehyde at a content of 0-30% by weight, n-valeraldehyde at a content of 0-90% by weight, hydrogen at a content of 0-50% by weight, carbon monoxide at a content of 0-50% by weight, cyclopropane at a content of 0-30% by weight, isobutane at a content of 0-50% by weight, n-butane at a content of 0-50% by weight, trans-2-butene at a content of 0-98% by weight, 1-butene at a content of 0-99% by weight, isobutene at a content of 0-15% by weight, and cis-2-butene at a content of 0-95% by weight.

[0052] In the present invention, the mixed butene hydroformylation reaction product is obtained by the following method: under hydroformylation reaction conditions, butene, H2 and CO are contacted and reacted.

[0053] In the present invention, preferably, the hydroformylation reaction conditions include: a reaction temperature of 80-120° C., preferably 90-110° C.; and a reaction pressure of 0.5-5 MPa, preferably 1.5-3 MPa.

[0054] In the present invention, the reaction is carried out in the presence of a catalyst. Preferably, the catalyst is dissolved in an organic solvent.

[0055] In the present invention, the catalyst is a rhodium-phosphine complex catalyst obtained by complexing a rhodium-containing compound with an organic phosphine ligand.

[0056] Preferably, the rhodium-containing compound in the rhodium-phosphine complex catalyst is at least one selected from rhodium dicarbonyl acetylacetonate, rhodium trioxide, tetrarhodium dodecacarbonyl, hexarhodium hexadecane, rhodium nitrate and rhodium acetate.

[0057] Preferably, the phosphine ligand in the rhodium-phosphine complex catalyst is selected from at least one of trialkylphosphines, triarylphosphines, alkyldiarylphosphines, dialkylarylphosphines, dicycloalkylarylphosphines, cycloalkyldiarylphosphines, triaralkylphosphines, tricycloalkylhexylphosphines and alkyl and / or aryldiphosphines, monoorganophosphites, diorganophosphites and phosphates.

[0058] In the present invention, preferably, the organic solvent is selected from at least one of alkanes and their derivatives, aromatic hydrocarbons and their derivatives, alcohols and their derivatives, ketones and their derivatives, ethers and their derivatives, esters and their derivatives, sulfoxides and their derivatives, and phenols and their derivatives.

[0059] Preferably, the aromatic hydrocarbons and their derivatives, alcohols and their derivatives, ketones and their derivatives, ethers and their derivatives, esters and their derivatives, sulfoxides and their derivatives, and phenols and their derivatives contain a carbon chain with 1 to 30 carbon atoms.

[0060] Preferably, the alkane and its derivatives have 6-30 carbon atoms.

[0061] In the present invention, preferably, the gas chromatography analysis equipment further comprises a vaporization chamber, and the temperature of the vaporization chamber is 240-260°C.

[0062] In the present invention, preferably, the carrier gas is selected from helium or argon; more preferably helium

[0063] In the present invention, in order to further improve the accuracy of the analysis results, preferably, n=3, and the conditions for detecting and analyzing the liquid phase in the mixed butene hydroformylation reaction product by the gas chromatography analysis method include: dwelling at a column temperature of 35-45°C for 2-4 minutes, raising the column temperature to 90-110°C at a rate of 8-12°C / min, dwelling for 15-25 minutes, then raising the column temperature to 170-190°C at a rate of 18-22°C / min, dwelling for 4-7 minutes, and the detector temperature is 240-260°C.

[0064] In the present invention, in order to further improve the accuracy of the analysis results, preferably, n=3, and the conditions for the gas chromatography analysis method for detecting and analyzing the gas phase in the mixed butene hydroformylation reaction product include: dwelling at a column temperature of 100-120°C for 25-35 minutes, raising the column temperature to 170-190°C at 8-12°C / min, dwelling for 8-12 minutes, and a detector temperature of 240-260°C.

[0065] According to a particularly preferred embodiment of the present invention, the method comprises:

[0066] (1) A gas chromatography analysis apparatus comprises chromatographic columns 1-n connected in series, wherein chromatographic columns 2 to chromatographic columns n are each equipped with an injection valve, and the injection valve is capable of sealing a gas component that first passes through the injection valve in the chromatographic column equipped with the injection valve and allowing a gas component that passes through the injection valve later to enter the next chromatographic column, a liquid phase injection port 6 and a first injection valve are provided upstream of chromatographic column 1, and chromatographic columns 1 to chromatographic columns n are each individually connected to a detector, wherein n is a natural number ranging from 3 to 5;

[0067] The gas phase in the mixed butene hydroformylation reaction product is carried into chromatographic column 1 by the carrier gas helium entering from the first injection valve and separated into n groups of gas components. The n-1 group of gas components that first flow out of chromatographic column 1 are sequentially adsorbed on chromatographic columns 2 to chromatographic column n and sealed.

[0068] (2) The aldehyde gas component that flows out from the chromatographic column 1 last is carried by the carrier gas into the detector for analysis (normalization analysis);

[0069] Then, the injection valves configured for chromatographic columns 2 to n are adjusted respectively so that the sealed gas components enter the detector for detection (normalization analysis);

[0070] Among them, when analyzing the components in the gas phase, the operating conditions of the gas chromatography analysis equipment include:

[0071] The stationary phase of the chromatographic column 1 is 5% phenyl-95% methylpolysiloxane or poly(dimethylsiloxane)poly(1,4-bis(dimethylsiloxy)arylene)siloxane, and the length of the chromatographic column 1 is 55-60 m, the inner diameter is 0.4-0.53 m, and the film thickness is 3-5 μm;

[0072] The stationary phase of chromatographic column 2 is selected from 5A molecular sieve, carbon molecular sieve or polystyrene divinylbenzene, the column length is 30-35m, the inner diameter is 0.4-0.53mm, and the film thickness is 23-28μm;

[0073] The stationary phase of the chromatographic column n is selected from sodium sulfate deactivated alumina, alumina or divinylbenzene / ethylene glycol dimethacrylate, the column length is 48-52m, the inner diameter is 0.4-0.53μm, and the film thickness is 0.13-0.18μm;

[0074] The column temperature was kept at 105-115°C for 28-32 minutes, then the column temperature was increased at a rate of 8-12°C / min to 175-185°C and kept there for 8-12 minutes; the vaporization temperature was 245-250°C, and the detector temperature was 245-255°C.

[0075] Alternatively, the liquid phase in the mixed butene hydroformylation reaction product is vaporized in the vaporization chamber and then carried into the chromatographic column 1 by the carrier gas helium entering from the first injection valve to separate into n groups of gas components. The analysis is performed according to the method for analyzing the gas phase in the mixed butene hydroformylation reaction product. The difference is that when analyzing the components in the liquid phase, the operating conditions of the gas chromatography analysis equipment include:

[0076] Keep the column at 38-42℃ for 2-4min, then increase the column temperature to 95-105℃ at 8-12℃ / min, and keep

[0077] 18-22min, then the column temperature is increased to 175-185℃ at 18-22℃ / min, and stays for 4-6min. The vaporization temperature is 245-250℃, and the detector temperature is 245-255℃.

[0078] The present invention will be described in detail below through examples.

[0079] In the following examples, the content of each component was analyzed by normalization method, that is, the ratio of the peak area of ​​each component in the chromatogram to the sum of the peak areas of each component in the chromatogram.

[0080] Example 1-1

[0081] (1) preparing a mixture simulating the gas phase in a mixed butene hydroformylation reaction product by mixing 0.36 parts by weight of methane, 12.06 parts by weight of isovaleraldehyde, 21.72 parts by weight of n-valeraldehyde, 0.05 parts by weight of hydrogen, 0.76 parts by weight of carbon monoxide, 0.02 parts by weight of cyclopropane, 0.60 parts by weight of isobutane, 1.41 parts by weight of n-butane, 1.63 parts by weight of trans-2-butene, 5.52 parts by weight of 1-butene, 0.64 parts by weight of nitrogen, and 0.83 parts by weight of cis-2-butene to obtain a simulated gas phase in a mixed butene hydroformylation reaction product;

[0082] (2) Figure 2As shown, the gas chromatography analysis equipment contains a chromatographic column 1, a chromatographic column 2 and a chromatographic column 3 connected in series, and the chromatographic column 2 and the chromatographic column 3 are each equipped with a six-way valve. A liquid phase injection port 6 and a first injection valve (six-way valve) are provided upstream of the chromatographic column 1. The first injection valve includes an inlet and an outlet for a gaseous sample, a quantitative tube, and a carrier gas inlet. A vaporization chamber is further provided between the chromatographic column 1 and the liquid phase injection port 5. The chromatographic column 1, the chromatographic column 2 and the chromatographic column 3 are respectively connected to a TCD detector 4 and an FID detector 5, and the TCD detector 4 and the FID detector 5 are connected in series.

[0083] The gas phase in the simulated mixed butene hydroformylation reaction product is injected from the inlet (injection port) of the first injection valve and quantified through the quantitative tube. The first injection valve is adjusted, and the gas phase in the quantitative tube is brought into the chromatographic column 1 by the carrier gas helium entering from the first injection valve for separation. After the aldehyde substances are separated, the remaining components first flow out of the chromatographic column 1, and the aldehyde substances flow out of the chromatographic column 1 last; the six-way valve configured for the chromatographic column 2 is adjusted, and the remaining components are brought into the chromatographic column 2 by the carrier gas helium for separation, among which nitrogen, hydrogen, carbon monoxide and methane enter the chromatographic column 2, and the six-way valve configured for the chromatographic column 2 is adjusted again to seal nitrogen, hydrogen, carbon monoxide and methane in the chromatographic column 2; the six-way valve configured for the chromatographic column 3 is adjusted, and the components (cyclopropane and C4 hydrocarbons) not sealed in the chromatographic column 2 are brought into the chromatographic column 3 by the carrier gas helium for separation, and the six-way valve configured for the chromatographic column 3 is adjusted again to seal cyclopropane and C4 hydrocarbons in the chromatographic column 3.

[0084] (3) After eluting from chromatographic column 1, the aldehydes were carried by the carrier gas helium into the FID for analysis (normalization method quantitative analysis, the same below). The analysis results are shown in Table 3;

[0085] The six-way valve configured for chromatographic column 2 was adjusted, and the components nitrogen, hydrogen, carbon monoxide, and methane sealed in chromatographic column 2 were carried into the detector TCD by the carrier gas helium for analysis. The analysis results are shown in Table 3. After the analysis was completed, the six-way valve configured for chromatographic column 2 was adjusted again to close chromatographic column 2;

[0086] The six-way valve of the chromatographic column 3 was adjusted, and the components sealed in the chromatographic column 3 were carried into the detector FID by the carrier gas helium for analysis. The analysis results are shown in Table 3;

[0087] The gas chromatogram of the gas phase in the hydroformylation reaction product of mixed butenes is shown in Figure 3 ;

[0088] The operating conditions of the gas chromatography equipment are shown in Table 1.

[0089] Example 1-2

[0090] (1) preparing a mixture simulating a liquid phase in a mixed butene hydroformylation reaction product by mixing 15.26 parts by weight of n-valeraldehyde, 0.045 parts by weight of hydrogen, 0.73 parts by weight of carbon monoxide, 1.10 parts by weight of isobutane, 2.50 parts by weight of n-butane, 14.21 parts by weight of trans-2-butene, 0.47 parts by weight of 1-butene, 0.21 parts by weight of isobutene, and 1.54 parts by weight of cis-2-butene to obtain a simulated liquid phase in a mixed butene hydroformylation reaction product;

[0091] (2) Figure 2 As shown, the gas chromatography analysis equipment of this embodiment is the same as that of Example 1-1. The liquid phase in the simulated mixed butene hydroformylation reaction product is sampled from the liquid phase inlet and vaporized in the vaporization chamber. After the liquid phase is vaporized, the carrier gas helium entering through the first injection valve (six-way valve) is brought into the chromatographic column 1 for separation. After the aldehyde substances are separated, the remaining components first flow out of the chromatographic column 1, and the aldehyde substances flow out of the chromatographic column 1 last; the six-way valve configured for the chromatographic column 2 is adjusted, and the remaining components are brought into the chromatographic column 2 by the carrier gas helium for separation, wherein nitrogen, hydrogen, carbon monoxide and methane enter the chromatographic column 2, and the six-way valve configured for the chromatographic column 2 is adjusted again to seal nitrogen, hydrogen, carbon monoxide and methane in the chromatographic column 2; the six-way valve configured for the chromatographic column 3 is adjusted, and the components not sealed in the chromatographic column 2 are brought into the chromatographic column 3 by the carrier gas N2 for subdivision, and the six-way valve configured for the chromatographic column 3 is adjusted again to seal the C4 hydrocarbons in the chromatographic column 3.

[0092] (3) After eluting from column 1, the aldehydes were carried by the carrier gas helium into the FID for analysis. The analysis results are shown in Table 4.

[0093] The six-way valve configured for chromatographic column 2 was adjusted, and the components nitrogen, hydrogen, carbon monoxide, and methane sealed in chromatographic column 2 were carried into the detector TCD by the carrier gas helium for analysis. The analysis results are shown in Table 4. After the analysis was completed, the six-way valve configured for chromatographic column 2 was adjusted again to close chromatographic column 2;

[0094] The six-way valve of the chromatographic column 3 was adjusted, and the components sealed in the chromatographic column 3 were carried into the detector FID by the carrier gas helium for analysis. The analysis results are shown in Table 4;

[0095] The gas chromatogram of the liquid phase in the mixed butene hydroformylation reaction product is shown in Figure 4 ;

[0096] The operating conditions of the gas chromatography equipment are shown in Table 2.

[0097] Comparative Example 1

[0098] Detection was performed according to the method of Example 1-1, except that two chromatographic columns were connected in series, wherein chromatographic column 1 was an HP-AL / S (alumina stationary phase deactivated by sodium sulfate) chromatographic column, chromatographic column 1 was 40 m long, 0.3 mm in inner diameter, 5 μm in film thickness, and was connected to an FID detector; chromatographic column 2 was a TDX-01 (carbon molecular sieve stationary phase) chromatographic column, chromatographic column 2 was 2 m long, 0.2 mm in inner diameter, and was connected to a TCD detector; the FID and TCD detectors were connected in parallel, wherein aldehydes, cyclopropane, and C4 hydrocarbons entered the FID detector for detection; and nitrogen, hydrogen, carbon monoxide, and methane entered the TCD detector for detection. The detection results (peak area percentage %) are as follows: H2 (25.59), nitrogen (1.55), CO (1.85), methane (0.32), cyclopropane (0.12), isobutane (4.26), n-butane (9.94), trans-2-butene (11.53), 1-butene (39.00), cis-2-butene (5.84).

[0099] Comparative Example 2

[0100] Detection was performed according to the method of Example 1-1, except that a single chromatographic column was used. Column 1 was a SE-30 quartz capillary column with a length of 50 m, an inner diameter of 0.2 mm, and a film thickness of 0.5 μm, connected to an FID detector. The analysis results (peak area percentage %) were: isobutane (4.72), n-butane (10.74), isobutylene (0.84), trans-2-butene (61.09), 1-butene (2.02), cis-2-butene (6.61), and n-valeraldehyde (13.98).

[0101] Table 1

[0102]

[0103] Table 2

[0104]

[0105]

[0106] Table 3

[0107] Serial number Retention time min Compound Peak area content (%) 1 2.734 hydrogen 25.443 2 3.494 methane 0.323 3 3.878 Isovaleraldehyde 0.206 4 4.001 n-Valeraldehyde 0.362 5 4.145 Nitrogen 1.544 6 6.619 carbon monoxide 1.840 7 7.474 Cyclopropane 0.118 8 8.178 Isobutane 4.232 9 8.518 n-butane 9.879 10 10.045 trans-2-butene 11.468 11 10.189 1-Butene 38.777 12 11.358 cis-2-butene 5.808

[0108] Table 4

[0109] Serial number Retention time min Compound Peak area content (%) 1 10.63 Valve switching signal 12.671 n-Valeraldehyde 13.877 2 29.448 hydrogen 0.308 3 32.105 carbon monoxide 0.409 4 35.112 Valve switching signal 5 35.990 Isobutane 4.685 6 36.560 n-butane 10.659 7 37.761 Isobutylene 0.836 8 39.343 trans-2-butene 60.653 9 39.631 1-Butene 2.01 10 40.666 cis-2-butene 6.563

[0110] From the above results, it can be seen that compared with Comparative Example 1-1 using two chromatographic columns and detectors in parallel and Comparative Example 1-2 using the prior art, i.e., using one chromatographic column and an FID detector, the method of the present invention can realize the analysis of all components in the mixed butene hydroformylation reaction product in the same gas chromatography analysis equipment, without changing the configuration, it is possible to simultaneously analyze the components in the gas phase and the liquid phase of the mixed butene hydroformylation reaction product, the operation is simple and convenient, the separation is rapid, and the gas chromatogram ( Figure 3 and Figure 4 ) has sharp peaks without tailing, and the results are accurate, which can accurately reflect the changes in the composition of the reaction products during the mixed butene hydroformylation reaction and is very suitable for monitoring the mixed butene hydroformylation reaction process.

[0111] The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, various simple variations of the technical solution of the present invention may be made, including combining the various technical features in any other appropriate manner. These simple variations and combinations should also be regarded as disclosed in the present invention and fall within the scope of protection of the present invention.

Claims

1. A gas chromatography analysis method for mixed butene hydroformylation reaction products, characterized in that: The gas chromatography analysis method comprises: using a gas chromatography analysis device to detect and analyze the mixed butene hydroformylation reaction product; wherein the carrier gas brings the mixed butene hydroformylation reaction product into a chromatographic column 1 for separation, and two groups of gas components in the obtained gas components are adsorbed in chromatographic columns 2 to 3 in sequence according to the time of leaving the chromatographic column 1 and sealed, and then the injection valves configured in each chromatographic column are adjusted respectively so that the obtained gas components enter the detector for detection respectively; The gas chromatography analysis equipment comprises a chromatographic column and a detector, wherein the equipment comprises three chromatographic columns connected in series, wherein each of the chromatographic columns 2 to 3 is provided with an injection valve, and the injection valve can seal the gas components that first pass through the injection valve in the chromatographic column provided with the injection valve and allow the gas components that later pass through the injection valve to enter the next chromatographic column, and each chromatographic column is separately connected to the detector; Wherein, the stationary phase of the chromatographic column one is polysiloxane; the stationary phase of the chromatographic column two is selected from 5A molecular sieve, carbon molecular sieve, activated carbon, divinylbenzene nitrogen-containing heterocyclic monomer copolymer or polystyrene divinylbenzene; the stationary phase of the chromatographic column three is selected from at least one of potassium chloride deactivated alumina, sodium sulfate deactivated alumina, alumina and dimethylpolysiloxane; wherein the mixed butene hydroformylation reaction product contains at least one of methane, isovaleraldehyde, n-valeraldehyde, nitrogen, hydrogen, carbon monoxide, cyclopropane, isobutane, n-butane, trans-2-butene, 1-butene, isobutene and cis-2-butene; The conditions for detecting and analyzing the gas phase in the mixed butene hydroformylation reaction product by the gas chromatography analysis method include: staying at a column temperature of 35-45°C for 2-4 minutes, increasing the column temperature to 90-110°C at 8-12°C / min, staying for 15-25 minutes, then increasing the column temperature to 170-190°C at 18-22°C / min, staying for 4-7 minutes, and the detector temperature is 240-260°C; the conditions for detecting and analyzing the liquid phase in the mixed butene hydroformylation reaction product by the gas chromatography analysis method include: staying at a column temperature of 100-120°C for 25-35 minutes, increasing the column temperature to 170-190°C at 8-12°C / min, staying for 8-12 minutes, and the detector temperature is 240-260°C.

2. The gas chromatography analysis method according to claim 1, wherein: The chromatographic column 1 is also equipped with a first injection valve, which is used for gas phase injection in the mixed butene hydroformylation reaction product; And / or, the device further comprises a liquid phase injection port and a vaporization chamber, the liquid phase injection port is sequentially connected in series with the vaporization chamber and the chromatographic column, and the vaporization chamber is used to vaporize the liquid phase entering from the liquid phase injection port.

3. The gas chromatography analysis method according to claim 1 or 2, wherein: Chromatographic column 1 can separate the mixed butene hydroformylation reaction products into three or two gas components.

4. The gas chromatography analysis method according to claim 1 or 2, wherein: The stationary phase of the chromatographic column 1 is selected from 5% phenyl-95% methyl polysiloxane, 5% phenyl-95% dimethyl polysiloxane, 5% diphenyl-95% dimethyl polysiloxane, dimethyl polysiloxane, 5% diphenyl-1% vinyl-94% dimethyl polysiloxane or poly(dimethylsiloxane)poly(1,4-bis[dimethylsiloxy]arylene)siloxane; And / or, the length of the chromatographic column 1 is 30-60m, the inner diameter is 0.25-0.53mm, and the film thickness is 0.5-5μm; And / or, the stationary phase of the chromatographic column 2 is 5A molecular sieve; And / or, the length of the chromatographic column 2 is 30-60m, the inner diameter is 0.25-0.53mm, and the film thickness is 10-50μm; And / or, the stationary phase of the chromatographic column three is sodium sulfate deactivated alumina; And / or, the length of the chromatographic column three is 30-60m, the inner diameter is 0.25-0.53mm, and the film thickness is 0.10-15μm.

5. The gas chromatography analysis method according to claim 4, wherein: The stationary phase of the chromatographic column 1 is 5% phenyl-95% methyl polysiloxane or poly(dimethylsiloxane)poly(1,4-bis[dimethylsiloxy]arylene)siloxane.

6. The gas chromatography analysis method according to claim 4, wherein: The stationary phase of the chromatographic column 1 is poly(dimethylsiloxane)poly(1,4-bis[dimethylsiloxy]arylene)siloxane, the length of the chromatographic column 1 is 30-60m, the inner diameter is 0.25-0.53mm, and the film thickness is 0.5-5μm; And / or, the stationary phase of the chromatographic column 2 is 5A molecular sieve, the length of the chromatographic column 2 is 30-60m, the inner diameter is 0.25-0.53mm, and the film thickness is 10-50μm; And / or, the stationary phase of the chromatographic column three is sodium sulfate deactivated alumina, the length of the chromatographic column three is 30-60m, the inner diameter is 0.25-0.53mm, and the film thickness is 0.10-15μm.

7. The gas chromatography analysis method according to any one of claims 1, 2, 5 and 6, wherein: The injection valve is a six-way valve or a ten-way valve; And / or, the detector includes a TCD detector and a FID detector.

8. The gas chromatography analysis method according to claim 7, wherein: The injection valve is a six-way valve.

9. The gas chromatography analysis method according to claim 1, wherein: The chromatographic column one separates the mixed butene hydroformylation reaction products into three groups of gas components. The two groups of gas components that first flow out from the chromatographic column one are successively adsorbed in the chromatographic columns two to three and sealed. Then, the injection valves configured for the chromatographic columns two to three are adjusted respectively to allow the sealed gas components and the components that flow out last from the chromatographic column one to enter the detector for detection.

10. The gas chromatography analysis method according to any one of claims 1 or 9, wherein: The molecular weight of the components of the mixed butene hydroformylation reaction product is in the range of 2-120.

11. The gas chromatography analysis method according to claim 1 or 9, wherein: The gas chromatography analysis equipment also includes a vaporization chamber, and the temperature of the vaporization chamber is 240-260°C; And / or, the carrier gas is selected from argon or helium.

12. The gas chromatography analysis method according to claim 11, wherein: The carrier gas is helium.

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