CN114262257B - Method for recycling isoamyl alcohol through citral process waste liquid hydrogenation - Google Patents
Method for recycling isoamyl alcohol through citral process waste liquid hydrogenation Download PDFInfo
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- CN114262257B CN114262257B CN202010972599.0A CN202010972599A CN114262257B CN 114262257 B CN114262257 B CN 114262257B CN 202010972599 A CN202010972599 A CN 202010972599A CN 114262257 B CN114262257 B CN 114262257B
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- isoamyl alcohol
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- waste liquid
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- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 title claims abstract description 186
- 239000007788 liquid Substances 0.000 title claims abstract description 100
- 238000000034 method Methods 0.000 title claims abstract description 82
- 239000002699 waste material Substances 0.000 title claims abstract description 57
- 230000008569 process Effects 0.000 title claims abstract description 56
- WTEVQBCEXWBHNA-UHFFFAOYSA-N Citral Natural products CC(C)=CCCC(C)=CC=O WTEVQBCEXWBHNA-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229940043350 citral Drugs 0.000 title claims abstract description 47
- WTEVQBCEXWBHNA-JXMROGBWSA-N geranial Chemical compound CC(C)=CCC\C(C)=C\C=O WTEVQBCEXWBHNA-JXMROGBWSA-N 0.000 title claims abstract description 47
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 33
- 238000004064 recycling Methods 0.000 title claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 239000001257 hydrogen Substances 0.000 claims abstract description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 15
- 238000010168 coupling process Methods 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 239000012528 membrane Substances 0.000 claims description 64
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 46
- 238000001223 reverse osmosis Methods 0.000 claims description 35
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 26
- -1 isononyl ethoxychlorosilane Chemical compound 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 238000000926 separation method Methods 0.000 claims description 12
- 238000009835 boiling Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- AQZGPSLYZOOYQP-UHFFFAOYSA-N Diisoamyl ether Chemical compound CC(C)CCOCCC(C)C AQZGPSLYZOOYQP-UHFFFAOYSA-N 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 7
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 238000010926 purge Methods 0.000 claims description 5
- 239000002808 molecular sieve Substances 0.000 claims description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 3
- 238000007664 blowing Methods 0.000 claims description 2
- 238000004132 cross linking Methods 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 15
- 230000008878 coupling Effects 0.000 abstract description 5
- 238000005859 coupling reaction Methods 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 28
- CPJRRXSHAYUTGL-UHFFFAOYSA-N isopentenyl alcohol Chemical compound CC(=C)CCO CPJRRXSHAYUTGL-UHFFFAOYSA-N 0.000 description 14
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000010992 reflux Methods 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- FYRRWGUSDSVKRL-UHFFFAOYSA-N 2-methyl-4-(3-methylbut-3-enoxy)but-1-ene Chemical compound CC(=C)CCOCCC(C)=C FYRRWGUSDSVKRL-UHFFFAOYSA-N 0.000 description 4
- 229910000564 Raney nickel Inorganic materials 0.000 description 4
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000001760 fusel oil Substances 0.000 description 4
- QVDTXNVYSHVCGW-ONEGZZNKSA-N isopentenol Chemical compound CC(C)\C=C\O QVDTXNVYSHVCGW-ONEGZZNKSA-N 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 238000005371 permeation separation Methods 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 235000013599 spices Nutrition 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000000855 fermentation Methods 0.000 description 2
- 230000004151 fermentation Effects 0.000 description 2
- ZUBZATZOEPUUQF-UHFFFAOYSA-N isononane Chemical compound CCCCCCC(C)C ZUBZATZOEPUUQF-UHFFFAOYSA-N 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000010815 organic waste Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000005373 pervaporation Methods 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000000998 batch distillation Methods 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- SMRTZQCUWYSWJR-UHFFFAOYSA-N chloro(ethoxy)silane Chemical compound CCO[SiH2]Cl SMRTZQCUWYSWJR-UHFFFAOYSA-N 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 238000004868 gas analysis Methods 0.000 description 1
- 230000008570 general process Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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Abstract
The invention provides a method for recycling isoamyl alcohol by hydrogenating waste liquid of a citral process, which specifically comprises the following steps: introducing citral process waste liquid and hydrogen into a hydrogenation reactor filled with a hydrogenation catalyst, and reacting at a reaction temperature of 80-120 ℃ and a reaction pressure of 2.0-5.0 MPa to obtain a material flow containing isoamyl alcohol; isoamyl alcohol in the stream is recovered by direct rectification or rectification-permeation coupling. The method takes citral process waste liquid as a raw material to hydrogenate to obtain isoamyl alcohol material flow, and can directly rectify to obtain isoamyl alcohol products with purity more than 99 percent. The preferential rectification-permeation coupling process can remove moisture in the product to break multielement azeotropy, and then the high-quality isoamyl alcohol product (purity up to 99.9%) can be obtained with high recovery rate through simple rectification, and the method has the advantages of good stability of raw materials and process, high recovery efficiency and stable product quality, and can meet the high-end application requirements.
Description
Technical Field
The invention relates to a method for recycling isoamyl alcohol, in particular to a method for recycling isoamyl alcohol through the hydrogenation of waste liquid of a citral process.
Background
The isoamyl alcohol is an important chemical raw material, and is mainly applied to the production fields of essence and spice, medical intermediate, mineral separation medicament and the like, wherein the requirements on the purity of the isoamyl alcohol in the fields of the essence and the spice and the medical intermediate are relatively high, and the general requirements are more than 99.9 percent.
In the prior art, the isoamyl alcohol is obtained by rectifying and extracting the fusel oil which is a byproduct in the ethanol fermentation process, but the content of the isoamyl alcohol in the fusel oil which is a byproduct generally varies between 30 and 60 percent due to the differences of raw materials and technologies in an actual ethanol fermentation plant, so that the component stability of the fusel oil has great influence on the production of the isoamyl alcohol by rectifying and extracting, the quality is easy to fluctuate, and the downstream application is influenced. The applicant finds that a certain amount of C5 unsaturated compounds (such as isopentenol, isopentenyl aldehyde and the like) remain in the process waste liquid of citral, and a material flow rich in isoamyl alcohol can be obtained through hydrotreating, and an isoamyl alcohol product can be recovered; the raw material source is stable, the recovery amount of the isoamyl alcohol is large, and the method is a good way for industrially preparing the isoamyl alcohol. However, the hydrogenation liquid contains various impurities such as water, so that multiple azeotropes exist during rectification separation, the direct recovery efficiency is low, the product purity is difficult to reach more than 99.9%, and the high-end requirement is difficult to meet.
In the prior art, no report is found on the preparation of isoamyl alcohol from citral process waste liquid. For a system with multiple azeotropes, water is generally distilled and removed by adding a third component, products are collected from the bottom of the tower, and then the products are continuously distilled to improve the purity, so that the energy consumption is high, the process is complex, and a large amount of toxic and harmful organic solvents are used, so that the environment is polluted. Patent CN102260140a proposes a process for producing absolute ethyl alcohol by a rectification osmosis method, in which water molecules are selectively removed by a polyethylene nitrile/polypropylene alcohol composite membrane in a rectification tower, but in the scheme, an ethanol-water mixture needs to sequentially pass through a permeation separation assembly formed by 10 membrane pieces in series, so that the selective separation effect of organic matters with smaller molecular weight is poor, the temperature before each membrane piece is required to be kept consistent, multiple heat exchange and heating are required, the operation is complex and long, and the membrane separation efficiency is low. Patent CN101372442a proposes a technology of coupling and separating total reflux batch distillation and water jet decompression pervaporation, which is an intermittent operation, is difficult to be suitable for continuous separation operation, and has low production efficiency; and the condensation at the downstream of the decompression pervaporation is difficult, the energy consumption is high, the organic solvent is easy to diffuse to the other side of the membrane, the recovery rate is low, and the like.
Disclosure of Invention
The invention provides a method for recovering isoamyl alcohol through the hydrogenation of citral process waste liquid. The method takes citral process waste liquid as a raw material to hydrogenate to obtain isoamyl alcohol material flow, and can directly rectify to obtain isoamyl alcohol products with purity more than 99 percent. In a preferred embodiment, the method removes the moisture in the product by a rectification-permeation coupling method to break the multielement azeotropy, and then the isoamyl alcohol product with high quality (the purity is up to 99.9%) can be obtained with high recovery rate by simple rectification.
In order to solve the technical problems, the invention is realized by the following technical scheme:
a method for recycling isoamyl alcohol through the hydrogenation of citral process waste liquid, which comprises the steps of introducing citral process waste liquid and hydrogen into a hydrogenation reactor filled with a hydrogenation catalyst, and reacting at a reaction temperature of 80-120 ℃ and a reaction pressure of 2.0-5.0 MPa to obtain a material flow containing isoamyl alcohol; the isoamyl alcohol in the stream is then recovered by direct rectification or by rectification-permeation coupling.
The hydrogenation catalyst is a supported or unsupported nickel catalyst. Preferably Raney nickel catalyst, ni/Al 2 O 3 Catalyst, ni/SiO 2 A catalyst, etc.; the loading of the metallic nickel in the supported catalyst is preferably 40-45%.
The raw material airspeed of the citral process waste liquid is 0.5 to 1.5h -1 The space velocity of the raw material of the hydrogen is 1.5 to 3.0h -1 。
Further, the stream after the hydrogenation of the citral process waste liquid comprises the following components in percentage by mass:
4.5 to 22 percent of water, 75 to 90 percent of isoamyl alcohol, 0.5 to 2 percent of methanol, 0.2 to 1 percent of pentane, 0.3 to 2 percent of isoamyl ether and 0.5 to 2 percent of other miscellaneous components.
The waste liquid of the citral process can be the production waste liquid for preparing citral by condensing and rearranging isopentenol and isopentenol, and can also be the production waste liquid for hydroisomerization of isopentenol in the prior process for preparing citral, and the like.
In another preferred embodiment, the specific process of the direct rectification method is as follows: and (3) delivering the material flow obtained after the citral process waste liquid is hydrogenated to a rectifying tower, controlling the temperature of the tower kettle to be 132-136 ℃ and the temperature of the tower top to be 90-110 ℃ for direct rectification, and obtaining the isoamyl alcohol product in the tower kettle.
In another preferred embodiment, the rectification-permeation coupling method comprises the following specific processes:
1) Feeding a material flow obtained by hydrogenating the citral process waste liquid into a first rectifying tower, wherein the temperature of the tower top is set to 88-100 ℃, and the temperature of the tower bottom is set to 110-125 ℃, so that water and light components in the material flow form a multi-component azeotrope and migrate to the tower top; the light components in the multielement azeotrope except water mainly comprise isoamyl alcohol, methanol, pentane and the like;
2) A reverse osmosis membrane is obliquely arranged on the cross section of the top of the first rectifying tower, water molecules in the multi-element azeotrope penetrate through the lower surface of the reverse osmosis membrane and are condensed into liquid in a membrane tube, and the liquid flows out and is discharged obliquely downwards along the inner wall of the membrane tube; further, the included angle between the reverse osmosis membrane and the cross section of the top of the first rectifying tower is 30-45 degrees; the step is used for removing most of moisture in the azeotrope and breaking the azeotrope;
3) After passing through gaps among the reverse osmosis membrane tubes, light components and a small amount of water in the multielement azeotrope enter a dephlegmator above the top of the tower, the dephlegmator temperature is controlled to be 65-68 ℃, so that water with high boiling point and isoamyl alcohol are condensed into liquid and flow back to the first rectifying tower, other light components with low boiling point are still in a gaseous state, and the light components and the isoamyl alcohol are discharged to a waste liquid barrel after being further condensed, thereby realizing light-heavy separation in the system; the step is used for removing low-boiling-point light components in the material flow, and refluxing isoamyl alcohol in the azeotrope into the rectifying tower so as to facilitate the improvement of the recovery rate of the product;
4) Collecting heavy components (including isoamyl alcohol products and other heavy component impurities) in the tower kettle of the first rectifying tower, transferring the heavy components to the second rectifying tower, continuously rectifying and separating at the tower kettle temperature of 133-145 ℃ and the tower top temperature of 130-132 ℃, collecting the isoamyl alcohol products at the tower top, and discharging the heavy components in the tower kettle to a waste liquid barrel.
In a preferred embodiment, the upper end of the reverse osmosis membrane is communicated with a nitrogen purging device, and condensed water in the membrane tube is discharged in an accelerating way under the effect of nitrogen air supply, so that water in the multi-element azeotrope can be promoted to penetrate through the reverse osmosis membrane more quickly, and the azeotropic breaking rate is improved. Further, the nitrogen gas may be introduced at a rate of 10 to 30L/min.
In a preferred embodiment, the reverse osmosis membrane is an isononyl ethoxychlorosilane hydrophilically modified reverse osmosis membrane. The invention adopts isononyl ethoxy chlorosilane to carry out hydrophilic modification on the reverse osmosis membrane, and the introduced isononyl can also cooperate with oxygen-containing groups in the membrane to dredge isoamyl alcohol containing branched chains in a micro environment, so that the probability that the isoamyl alcohol stays on the surface of the membrane and becomes liquid in a critical way is reduced, the water with small molecules is not affected, hydrogen in the water is preferentially aggregated with oxygen on the surface of the membrane through intermolecular force and is condensed into liquid, and the liquid is discharged, thereby breaking azeotropy.
The specific preparation method of the hydrophilically modified reverse osmosis membrane comprises the following steps:
A. tetrabutyl titanate, glutaraldehyde, isononyl ethoxychlorosilane, polyvinyl alcohol and absolute ethyl alcohol are uniformly mixed, and then stirred and defoamed to prepare film forming liquid;
B. and immersing the molecular sieve membrane tube assembly in a membrane forming liquid, taking out, and crosslinking at 100-150 ℃ for 1-6 hours to prepare the hydrophilic modified reverse osmosis membrane.
Preferably, in the step A, the raw materials are mixed according to the mass parts:
0.5 to 2 parts of tetrabutyl titanate, 0.2 to 3 parts of glutaraldehyde, 1 to 5 parts of isononyl ethoxy chlorosilane, 1 to 10 parts of polyvinyl alcohol and 40 to 60 parts of absolute ethyl alcohol.
Compared with the process for preparing isoamyl alcohol by extracting and rectifying fusel oil, the method for preparing isoamyl alcohol by hydrogenating the waste liquid of the citral process has the advantages of good stability of the raw materials and the process, stable product quality, and capability of solving the problem of difficult treatment of the waste liquid of the citral byproduct, thereby being beneficial to improving economic benefit. In addition, in a preferred embodiment, the technology of coupling the hydrophilically modified reverse osmosis membrane and rectification can ensure that water in the multielement azeotrope is preferentially permeated and adsorbed on the inner wall of the membrane tube to form water drops so as to form liquid and discharge, and continuously pushes water in the flow to permeate through the membrane for permeation separation, thereby playing the roles of breaking azeotropy in the flow and continuously separating and purifying organic products; the isoamyl alcohol is blocked in the membrane due to polarity deviation and steric hindrance of the isoamyl, so that the problems of low recovery efficiency and poor product purity of the isoamyl alcohol in rectification caused by multielement azeotropy of an isoamyl alcohol-rich stream obtained by hydrogenating the citral byproduct waste liquid are overcome, and the high-end requirements of essence, spice, medical intermediates and the like can be met; meanwhile, after the hydrophilic modification of the reverse osmosis membrane, the high-efficiency separation and discharge of water can be realized only by blowing nitrogen gas to the inner wall of the membrane tube, so that the limitation that the pressure difference is formed at two sides of the membrane for separation by means of negative pressure operation in the rectification-permeation separation in the prior art is overcome, the energy consumption is reduced, the requirements on separation equipment and operation are also reduced, the problem that the rectification-permeation separation technology has poor selective separation effect on small organic molecules with little difference from water molecules is solved, and the industrial applicability is better.
Drawings
FIG. 1 is a general process flow diagram of the rectification-permeation coupling method of the present invention.
In the figure: 1. a first rectifying column; 2. a second rectifying column; 3. a dephlegmator; 4. a reverse osmosis membrane; 5. and (5) nitrogen purging.
Detailed Description
The invention will now be further illustrated by means of specific examples which are given solely by way of illustration of the invention and do not limit the scope thereof.
In the embodiment of the invention, the light component and the heavy component do not specifically refer to a certain component or a plurality of components, wherein the light component refers to the general name of all components vaporized at the rectification temperature, and the heavy component refers to the general name of components which are not vaporized at the rectification temperature and still remain in the tower kettle. Thus, the components in the light fraction and the heavy fraction in each step are related to the rectification conditions thereof.
Product gas chromatographic analysis conditions: agilent gas chromatograph, RTX-WAX column, holding at 50deg.C for 5min; raising the temperature to 80 ℃ at 10 ℃/min, and keeping for 5min; heating to 100deg.C at 10deg.C/min, and maintaining for 5min; heating to 160 ℃ at 10 ℃/min, and keeping for 15min.
The sources of materials, reagents in the following examples are shown in table 1 below:
TABLE 1 sources of materials, reagents
The following process waste liquid is obtained in batches from the citral production procedure of Wanhua chemical group Co., ltd:
citral process waste liquid a: 19.7% of water, 28.2% of isoamyl alcohol, 31.7% of isopentenyl alcohol, 9.3% of isopentenyl aldehyde, 8.2% of isopentenyl aldehyde, 0.8% of isopentenyl ether, 0.3% of pentane, 0.5% of isopentenyl alcohol, 0.7% of formaldehyde and 0.6% of other substances.
Citral process effluent B: 7.8% of water, 33.1% of isoamyl alcohol, 33.8% of isopentenyl alcohol, 10.7% of isopentenyl aldehyde, 9.4% of isopentenyl aldehyde, 1.7% of isopentenyl ether, 0.2% of pentane, 0.3% of isopentenyl alcohol, 1.6% of formaldehyde and 1.3% of other substances.
Citral process waste liquid C: 10.8% of water, 33.7% of isoamyl alcohol, 28.6% of isopentenyl aldehyde, 11.8% of isopentenyl aldehyde, 11.6% of isopentenyl aldehyde, 1.0% of isopentenyl ether, 0.4% of pentane, 0.2% of isopentenyl alcohol, 0.6% of formaldehyde and 1.3% of other materials.
Citral process waste liquid D: 13.2% of water, 26.5% of isoamyl alcohol, 34.9% of isopentenyl alcohol, 12.7% of isopentenyl aldehyde, 9.3% of isopentenyl aldehyde, 0.7% of isopentenyl ether, 0.2% of pentane, 0.4% of isopentenyl alcohol, 1.3% of formaldehyde and 0.8% of other substances.
Other reagents used in the following examples were all commercially available unless otherwise specified.
The batch process recovery rate calculation formula is: m is M Quality of isoamyl alcohol product *W Content of isoamyl alcohol ％*100％/(M Quality of hydrogenated liquid of process waste liquid *W Content of isoamyl alcohol ％)；
The calculation formula of the recovery rate of the continuous process is as follows: m is M Unit pilot production quality of isoamyl alcohol product *W Content of isoamyl alcohol ％*100％/(M Quality of hydrogenated liquid of process waste liquid per unit time *W Content of isoamyl alcohol ％)。
[ preparation example ]: preparation of hydrophilically modified reverse osmosis membranes
108g of ethoxychlorosilane, 0.5g of chloroplatinic acid and 100g of isopropanol were mixed, replaced with nitrogen, and then heated to 80℃under a nitrogen atmosphere, 132g of isononane was added to the system, and the mixture was stirred for 2 hours. After the reaction, distillation was carried out under reduced pressure, 217g of isononyl ethoxychlorosilane product was isolated in 92.3% yield. Elemental analysis of the product: c,55.78; h,10.64; cl,14.97; o,6.75; si,11.86; and (3) carrying out gas analysis on the product: 236.14 (100%); 238.13 (35.3%); 239.14 (4.4%).
Mixing and dissolving 10g of tetrabutyl titanate, 10g of glutaraldehyde, 20g of isononyl ethoxychlorosilane, 20g of polyvinyl alcohol and 50g of absolute ethyl alcohol, stirring for 5 hours at room temperature, and then vacuum defoaming to obtain viscous liquid, namely film forming liquid. And then immersing the molecular sieve membrane tube assembly in a membrane forming liquid for 3 hours, taking out, and then treating for 4 hours at 120 ℃ to obtain the hydrophilically modified reverse osmosis membrane.
[ example 1 ]
Introducing the citral process waste liquid A and hydrogen into a hydrogenation reactor filled with 100g of Raney nickel catalyst, and controlling the airspeed of the citral process waste liquid A to be 0.8h -1 Hydrogen space velocity of 2.0h -1 Reacting at 105 ℃ and 2.5MPa to obtain hydrogenated liquid containing isoamyl alcohol;
the gas phase analysis shows that the composition of the substances in the hydrogenation liquid is as follows: 19.7% of water, 77.4% of isoamyl alcohol, 0.8% of isoamyl ether, 0.8% of pentane, 0.7% of methanol and 0.6% of other impurity components.
500g of the hydrogenated material flow was fed into a first rectifying column for rectification (normal pressure, reflux ratio 5, column bottom temperature 133 ℃ C., column top temperature 94 ℃ C.). 203g of liquid is collected at the top of the tower, wherein the moisture content is 48.5%, the isoamyl alcohol is 46.7%, and the layering phenomenon exists; meanwhile, 297g of isoamyl alcohol product (purity 99.4%) was obtained in the column bottom, and the recovery rate of isoamyl alcohol was 75.7%.
[ example 2 ]
The citral process effluent B was fed with hydrogen gas with 100g Ni/Al 2 O 3 Catalyst (Ni-supported)42.7 percent of hydrogenation reactor, and controlling the space velocity of the process waste liquid B to be 0.5h -1 The hydrogen space velocity is 1.6h -1 Reacting at the reaction temperature of 90 ℃ and the reaction pressure of 3.5MPa to obtain hydrogenated liquid containing isoamyl alcohol;
the gas phase analysis shows that the composition of the substances in the hydrogenation liquid is as follows: 7.8% of water, 87.1% of isoamyl alcohol, 1.7% of isoamyl ether, 0.5% of pentane, 1.6% of methanol and 1.3% of other materials.
500g of the hydrogenated material flow was fed into a first rectifying column for rectification (normal pressure, reflux ratio: 5, rectification temperature: 134 ℃ C., overhead temperature: 104 ℃ C.). 107.3g of liquid, of which the moisture content is 36.4% and the isoamyl alcohol content is 45.1%, was collected at the top of the column and had a delamination phenomenon; at the same time, 392.7g of isoamyl alcohol product (purity 99.1%) is obtained in the tower kettle, and the recovery rate of the isoamyl alcohol is 88.0%.
[ example 3 ]
Introducing citral process waste liquid C and hydrogen into a reactor filled with 100g of Ni/SiO 2 Hydrogenation reactor of catalyst (Ni loading 43.8%) and control space velocity of process waste liquid C to 0.9h -1 Hydrogen space velocity of 2.0h -1 Reacting at the reaction temperature of 110 ℃ and the reaction pressure of 4.5MPa to obtain hydrogenated liquid containing isoamyl alcohol;
the gas phase analysis shows that the composition of the substances in the hydrogenation liquid is as follows: 10.8% of water, 85.7% of isoamyl alcohol, 1.0% of isoamyl ether, 0.6% of pentane, 0.6% of methanol and 1.3% of other.
According to the process route in fig. 1, the water in the hydrogenation liquid is removed by a rectification-permeation coupling method, and the specific operation is as follows:
1) Feeding 500g of hydrogenated material flow into a first rectifying tower 1, controlling the temperature of a tower kettle to 124 ℃, and controlling the temperature of a tower top to 98 ℃ so that water and light components in the material flow form a multi-element azeotrope and migrate to the tower top;
2) A reverse osmosis membrane 4 which forms an included angle of 30 degrees with the horizontal plane is obliquely arranged on the cross section of the top of the first rectifying tower, water molecules in the multielement azeotrope penetrate through the lower surface of the reverse osmosis membrane and are condensed into liquid in a membrane tube, and the liquid flows out and is discharged obliquely downwards along the inner wall of the membrane tube under nitrogen purging 5;
3) After passing through gaps among the reverse osmosis membrane tubes, light components and a small amount of water in the multielement azeotrope enter a dephlegmator 3 above the top of the tower, the dephlegmator temperature is controlled to be 65 ℃, so that water with high boiling point and isoamyl alcohol are condensed into liquid and flow back to the first rectifying tower, and other light components with low boiling point are condensed at a temperature of 25 ℃ and then are recycled to a waste liquid barrel;
4) And collecting heavy components (including isoamyl alcohol products and other heavy component impurities) in the tower kettle of the first rectifying tower, transferring the heavy components to the second rectifying tower 2, continuously rectifying and separating under the conditions of the tower kettle temperature of 138.6 ℃, the tower top temperature of 131.4 ℃, normal pressure and reflux ratio of 2, collecting the isoamyl alcohol products at the tower top, and discharging the heavy components in the tower kettle to a waste liquid barrel.
After the rectification is finished, 54g of liquid is collected from the reverse osmosis membrane; 6.2g of the collected organic waste liquid is condensed at 25 ℃ in a dephlegmator; 420.4g (purity 99.9%) of isoamyl alcohol product is collected from the top of the second rectifying tower, 19.4g of heavy component waste liquid is obtained from the tower kettle, and the recovery rate of the isoamyl alcohol is 98.1%.
[ example 4 ]
Introducing the citral process waste liquid D and hydrogen into a hydrogenation reactor filled with 100g of Raney nickel catalyst, and controlling the airspeed of the citral process waste liquid D to be 1.0h -1 The hydrogen space velocity is 2.5h -1 Reacting at the reaction temperature of 120 ℃ and the reaction pressure of 3.0MPa to obtain hydrogenated liquid containing isoamyl alcohol;
the gas phase analysis shows that the composition of the substances in the hydrogenation liquid is as follows: 13.2% of water, 83.4% of isoamyl alcohol, 0.7% of isoamyl ether, 0.6% of pentane, 1.3% of methanol and the other 0.8%.
The hydrogenation solution was subjected to rectification-osmotic coupling separation in the same manner as in example 1, except that: 1) The included angle between the reverse osmosis membrane and the horizontal plane is 45 degrees; 2) The temperature of the top of the first rectifying tower is 94 ℃, and the temperature of the bottom of the first rectifying tower is 123.6 ℃; 3) The temperature of the top of the second rectifying tower is 131.2 ℃ and the temperature of the bottom of the tower is 137.5 ℃.
After the rectification is finished, 66.3g of liquid is collected from the reverse osmosis membrane; 9.9g of the collected organic waste liquid is condensed at 25 ℃ in a dephlegmator; 406.8g (purity 99.7%) of isoamyl alcohol product is collected at the top of the second rectifying tower, 17g of heavy component waste liquid is obtained at the bottom of the tower, and the recovery rate of the isoamyl alcohol is 97.3%.
[ example 5 ]
Introducing the citral process waste liquid A and hydrogen into a hydrogenation reactor filled with 100g of Raney nickel catalyst, and controlling the airspeed of the citral process waste liquid A to be 1.2h -1 Hydrogen space velocity of 2.0h -1 Reacting at the reaction temperature of 100 ℃ and the reaction pressure of 3.0MPa to obtain hydrogenated liquid containing isoamyl alcohol;
the gas phase analysis shows that the composition of the substances in the hydrogenation liquid is as follows: 19.7% of water, 77.4% of isoamyl alcohol, 0.8% of isoamyl ether, 0.8% of pentane, 0.7% of methanol and the other 0.6%.
The method for removing the water in the hydrogenation liquid by the rectification-permeation coupling method in the continuous process comprises the following specific processes:
1) Continuously adding the hydrogenated material flow into a first rectifying tower at a position 2/3 away from the tower kettle of the first rectifying tower at a feeding speed of 2Kg/h, controlling the temperature of the tower kettle to 116 ℃, controlling the temperature of the tower top to 91.6 ℃, and enabling water and light components in the material flow to form a multi-component azeotrope to migrate towards the tower top;
2) A reverse osmosis membrane which forms an included angle of 35 degrees with the horizontal plane is obliquely arranged on the cross section of the top of the first rectifying tower, water molecules in the multielement azeotrope are condensed into liquid in a membrane tube after penetrating through the lower surface of the reverse osmosis membrane, and flow out and are discharged obliquely downwards along the inner wall of the membrane tube under nitrogen purging;
3) After passing through gaps among the reverse osmosis membrane tubes, light components and a small amount of water in the multielement azeotrope enter a dephlegmator above the top of the tower, the dephlegmator temperature is controlled to be 65 ℃, so that water with high boiling point and isoamyl alcohol are condensed into liquid and flow back to the first rectifying tower, and other light components with low boiling point are condensed at a temperature of 25 ℃ and then are recycled to a waste liquid barrel;
4) Simultaneously, heavy components (including isoamyl alcohol products and other heavy component impurities) in the tower kettle of the first rectifying tower enter the second rectifying tower at a speed of 1573g/h at a position which is 1/2 away from the tower kettle of the second rectifying tower, continuously rectifying and separating under the conditions of a tower kettle temperature of 137.8 ℃, a tower top temperature of 131.6 ℃, normal pressure and a reflux ratio of 2, continuously collecting the tower top to obtain 1508.4g/h (purity of 99.9%) of the isoamyl alcohol products, continuously discharging the heavy components in the tower kettle to a waste liquid barrel at a speed of 64.6g/h, and realizing an isoamyl alcohol recovery rate of 97.3%.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that modifications and additions may be made to those skilled in the art without departing from the method of the present invention, which modifications and additions are also to be considered as within the scope of the present invention.
Claims (8)
1. A method for recycling isoamyl alcohol through the hydrogenation of citral process waste liquid is characterized in that the citral process waste liquid and hydrogen are fed into a hydrogenation reactor filled with a hydrogenation catalyst to react at the reaction temperature of 80-120 ℃ and the reaction pressure of 2.0-5.0 MPa to obtain a material flow containing isoamyl alcohol;
recovering isoamyl alcohol in the material flow by a rectification-permeation coupling method;
the specific process of the rectification-permeation coupling method is as follows:
1) Feeding a material flow obtained by hydrogenating the citral process waste liquid into a first rectifying tower, wherein the temperature of the top of the tower is set to 88-100 ℃, so that water and light components in the material flow form a multi-element azeotrope and migrate to the top of the tower;
2) A reverse osmosis membrane is obliquely arranged on the cross section of the top of the first rectifying tower, water molecules in the multi-element azeotrope penetrate through the lower surface of the reverse osmosis membrane and are condensed into liquid in a membrane tube, and the liquid flows out and is discharged obliquely downwards along the inner wall of the membrane tube;
3) After passing through gaps among the reverse osmosis membrane tubes, light components and a small amount of water in the multielement azeotrope enter a dephlegmator above the top of the tower, the dephlegmator temperature is controlled to be 65-68 ℃, so that water with high boiling point and isoamyl alcohol are condensed into liquid and flow back to the first rectifying tower, other light components with low boiling point are still in a gaseous state, and light-weight separation is realized through the dephlegmator;
4) Collecting heavy components in the tower kettle of the first rectifying tower, transferring the heavy components to a second rectifying tower, continuously rectifying and separating at the temperature of the tower kettle of 133-145 ℃, and collecting the top of the tower to obtain an isoamyl alcohol product;
the reverse osmosis membrane is a hydrophilic modified reverse osmosis membrane of isononyl ethoxychlorosilane;
the preparation method of the reverse osmosis membrane comprises the following steps:
A. tetrabutyl titanate, glutaraldehyde, isononyl ethoxychlorosilane, polyvinyl alcohol and absolute ethyl alcohol are uniformly mixed, and then stirred and defoamed to prepare film forming liquid;
B. and immersing the molecular sieve membrane tube assembly in a membrane forming liquid, taking out, and crosslinking at 100-150 ℃ for 1-6 hours to prepare the hydrophilic modified reverse osmosis membrane.
2. The method for recovering isoamyl alcohol by the hydrogenation of citral process waste liquid according to claim 1, wherein the stream after the hydrogenation of citral process waste liquid comprises the following components in mass fraction:
4.5 to 22 percent of water, 75 to 90 percent of isoamyl alcohol, 0.5 to 2 percent of methanol, 0.2 to 1 percent of pentane, 0.3 to 2 percent of isoamyl ether and 0.5 to 2 percent of other miscellaneous components.
3. The method for recovering isoamyl alcohol by hydrogenating waste liquid in citral process according to claim 1, wherein the angle between the reverse osmosis membrane and the cross section of the top of the first rectifying tower is 30-45 °.
4. A method for recovering isoamyl alcohol by the hydrogenation of a waste liquid from a citral process according to any one of claims 1 to 3 wherein the light components of said multicomponent azeotrope other than water mainly comprise isoamyl alcohol, methanol, pentane.
5. The method for recovering isoamyl alcohol by hydrogenating waste liquid in citral process according to any one of claims 1 to 3, wherein the upper end of the reverse osmosis membrane is communicated with a nitrogen purging device, and condensed water in the membrane tube is discharged under the action of nitrogen blowing to promote water in the multi-element azeotrope to pass through the reverse osmosis membrane more quickly, so that the azeotropic breaking rate is improved.
6. The method for recycling isoamyl alcohol by hydrogenating waste liquid in citral process according to claim 1, wherein in the step A, the raw materials are mixed according to the mass parts:
0.5 to 2 parts of tetrabutyl titanate, 0.2 to 3 parts of glutaraldehyde, 1 to 5 parts of isononyl ethoxy chlorosilane, 1 to 10 parts of polyvinyl alcohol and 40 to 60 parts of absolute ethyl alcohol.
7. The method for recovering isoamyl alcohol by hydrogenating waste liquid from citral process according to claim 1, wherein the hydrogenation catalyst is a supported or unsupported nickel-based catalyst.
8. The method for recovering isoamyl alcohol by the hydrogenation of citral process waste liquid according to claim 1, wherein the raw material space velocity of the citral process waste liquid is 0.5 to 1.5h -1 The space velocity of the raw material of the hydrogen is 1.5 to 3.0h -1 。
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