CN116555789A - Electrolyte for preparing adiponitrile by electrocatalytic acrylonitrile and electrolysis method - Google Patents
Electrolyte for preparing adiponitrile by electrocatalytic acrylonitrile and electrolysis method Download PDFInfo
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- CN116555789A CN116555789A CN202210102964.1A CN202210102964A CN116555789A CN 116555789 A CN116555789 A CN 116555789A CN 202210102964 A CN202210102964 A CN 202210102964A CN 116555789 A CN116555789 A CN 116555789A
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- acrylonitrile
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 52
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 title claims abstract description 48
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000005868 electrolysis reaction Methods 0.000 title abstract description 4
- 150000004714 phosphonium salts Chemical group 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 claims abstract description 4
- 150000001768 cations Chemical class 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 12
- 229910021538 borax Inorganic materials 0.000 claims description 10
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 10
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 10
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 10
- 239000004328 sodium tetraborate Substances 0.000 claims description 10
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 10
- 229910019142 PO4 Inorganic materials 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 8
- 239000010452 phosphate Substances 0.000 claims description 8
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 6
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- 229910000975 Carbon steel Inorganic materials 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 150000001450 anions Chemical class 0.000 claims description 3
- -1 bis (trifluoromethanesulfonyl) imide anions Chemical class 0.000 claims description 3
- 239000010962 carbon steel Substances 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 claims description 3
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 3
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- YEXPOXQUZXUXJW-UHFFFAOYSA-N lead(II) oxide Inorganic materials [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims description 3
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 3
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 3
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 3
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 3
- 235000011009 potassium phosphates Nutrition 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 3
- 239000001488 sodium phosphate Substances 0.000 claims description 3
- 235000011008 sodium phosphates Nutrition 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 159000000001 potassium salts Chemical class 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 239000000243 solution Substances 0.000 description 7
- 238000006471 dimerization reaction Methods 0.000 description 6
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical class [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 description 6
- 229920002302 Nylon 6,6 Polymers 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000004176 ammonification Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/01—Products
- C25B3/09—Nitrogen containing compounds
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention provides an electrolyte for preparing adiponitrile by electrocatalytic acrylonitrile and an electrolysis method. Wherein the electrolyte comprises acrylonitrile, modified quaternary phosphonium salt and water, the cation of the modified quaternary phosphonium salt is a group shown in a formula (a 1) or a formula (b 1) which is connected at one end of the structure of the formula (f), and a group shown in a formula (a 1), (b 1), (c), (d) or (e) is connected at the other end of the structure of the modified quaternary phosphonium salt;wherein R is 2 ～R 22 Each independently is a C1-C5 alkyl group; n=1 to 6. Compared with the traditional quaternary ammonium salt, the electrolyte for preparing adiponitrile by electrolyzing acrylonitrile disclosed by the invention has the advantages that the use of the quaternary phosphonium salt improves the selectivity of the target product adiponitrile, so that the electrolyte has a better economic effect.
Description
Technical Field
The invention relates to the field of electrochemical synthesis, and discloses a method for synthesizing adiponitrile from acrylonitrile.
Background
Adiponitrile (ADN) is an important organic chemical intermediate, and is mainly used for producing materials such as polyhexamethylene adipamide (nylon 66), 1, 6-Hexamethylene Diisocyanate (HDI), nylon 610 and the like. About 90% of adiponitrile is statistically used worldwide to produce nylon 66 each year. The process comprises the steps of hydrogenation of adiponitrile to produce hexamethylenediamine, and polycondensation of hexamethylenediamine and adipic acid to obtain a semitransparent or opaque milky synthetic resin (nylon 66).
The adiponitrile technology has higher barriers and investment thresholds and extremely high industrial concentration. The adiponitrile industrial production technology comprises AN adipic acid catalytic ammonification method (ADA), AN acrylonitrile electrolytic dimerization method (AN) and a butadiene cyanidation method (BD).
The electrolytic dimerization of acrylonitrile uses acrylonitrile as raw material and uses electrochemical method to dimerize adiponitrile. The process for preparing adiponitrile by electrolytic dimerization of acrylonitrile has the characteristics of short flow, high product quality and the like. However, the main component used in the traditional electrolyte for adjusting the reaction selectivity is quaternary ammonium salt, the quaternary ammonium salt is used in a large amount, and the cost is high, so that the cost of the electrolytic dimerization of acrylonitrile is increased.
Disclosure of Invention
In order to solve the problems, the invention provides an electrolyte for preparing adiponitrile by electrolyzing acrylonitrile and a preparation method thereof.
The invention provides an electrolyte for preparing adiponitrile by electrocatalytic acrylonitrile, which comprises acrylonitrile, modified quaternary phosphonium salt and water, wherein the cation of the modified quaternary phosphonium salt is a group shown in a formula (a 1) or a formula (b 1) which is connected with one end of a structure shown in a formula (f), and the other end of the structure is connected with a group shown in a formula (a 1), (b 1), (c), (d) or (e);
wherein R is 2 ～R 22 Each independently is a C1-C5 alkyl group; n=1 to 6.
According to an embodiment of the present invention, the content of the modified quaternary phosphonium salt in the electrolytic solution is 0.01 to 3wt%, preferably 0.01 to 1wt%.
According to another embodiment of the invention, the anion of the modified quaternary phosphonium salt is one or more of hydroxide, bisulfate, sulfate, phosphate, hydrogen phosphate, dihydrogen phosphate, acetate, nitrate, bis (trifluoromethanesulfonyl) imide anions.
According to another embodiment of the invention, the electrolyte further contains 0.1 to 10wt% of EDTA or sodium or potassium salts thereof, and 0.01 to 5wt% of borax.
According to another embodiment of the present invention, the electrolyte further comprises 1 to 20wt% of a phosphate salt, which is at least one of potassium phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, sodium phosphate, disodium hydrogen phosphate, and sodium dihydrogen phosphate.
According to another embodiment of the present invention, the acrylonitrile content in the electrolyte is 4 to 7wt%.
According to another embodiment of the invention, n is 4 to 6, R 2 ～R 12 Each independently is a C2-C4 alkyl group.
In another aspect, the invention provides a method for preparing adiponitrile by electrolyzing acrylonitrile, which adopts the electrolyte to carry out electrolytic reaction.
According to one embodiment of the invention, the cathode of the electrolytic reaction is Cd or Pb or alloy thereof, and the anode is carbon steel or stainless steel or PbO 2 。
According to another embodiment of the present invention, the reaction temperature of the electrolytic reaction is 30 to 70 ℃ and the current density is 200 to 5000A/m 2 。
Compared with the traditional quaternary ammonium salt, the electrolyte for preparing adiponitrile by electrolyzing acrylonitrile disclosed by the invention has the advantages that the use of the quaternary phosphonium salt improves the selectivity of the target product adiponitrile, so that the electrolyte has a better economic effect.
Detailed Description
The present invention will be described in detail with reference to the following embodiments.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The electrolyte for preparing adiponitrile from acrylonitrile by electrocatalytic catalysis comprises acrylonitrile, modified quaternary phosphonium salt and water, wherein the cation of the modified quaternary phosphonium salt is a group shown in a formula (a 1) or a formula (b 1) which is connected to one end of a structure in a formula (f), and the other end of the structure is connected to a group shown in a formula (a 1), (b 1), (c), (d) or (e);
wherein R is 2 ～R 22 Each independently is a C1-C5 alkyl group; n=1 to 6.
The inventors have found that the electrolyte contains a modified quaternary phosphonium salt to increase adiponitrile selectivity. The mechanism is not completely clear at present, and the possible action mechanism is that quaternary phosphonium salt is adsorbed on the surface of an electrode, so that the probability of further hydrogenation of acrylonitrile after the activation on the surface of the electrode to generate byproduct propionitrile is reduced. Thus, better selectivity of the target product can be obtained.
In an alternative embodiment, the modified quaternary phosphonium salt is present in an amount of 0.01 to 3wt%. When the content of the modified quaternary phosphonium salt in the electrolyte is less than 0.01wt%, the content of the modified quaternary phosphonium salt is low and is insufficient to significantly influence the conversion rate and the selectivity of the electrolytic dimerization reaction of acrylonitrile; if the content is more than 3wt%, the content of the modified quaternary phosphonium salt is too high, resulting in high use cost. Any number within the above range may be selected by one of skill in the art, such as, but not limited to, 0.0wt%, 0.05wt%, 0.1wt%, 0.5wt%, 1wt%, 1.5wt%, 2wt%, 2.5wt%, 3wt%, etc. The content of the modified quaternary phosphonium salt in the electrolyte is preferably 0.01 to 1wt%.
In alternative embodiments, the anion of the modified quaternary phosphonium salt is one or more of hydroxide, bisulfate, sulfate, phosphate, hydrogen phosphate, dihydrogen phosphate, acetate, nitrate, bis (trifluoromethanesulfonyl) imide anions.
In an alternative embodiment, the electrolyte may further contain EDTA or its sodium or potassium salt in an amount of 0.1 to 10wt% and borax in an amount of 0.01 to 5wt% in order to improve the electrolytic efficiency.
In an alternative embodiment, the electrolyte may further contain 1-20wt% of a phosphate, where the phosphate is at least one of potassium phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, sodium phosphate, disodium hydrogen phosphate, and sodium dihydrogen phosphate. The phosphate serves to adjust the pH of the electrolyte and the appropriate phosphate content may be selected to achieve the desired pH according to actual needs, for example, the phosphate concentration may be, but is not limited to, 1wt%, 5wt%, 10wt%, 15wt%, 20wt%, etc.
In an alternative embodiment, the acrylonitrile content is 4 to 7wt%. When the content of acrylonitrile in the electrolyte is less than 4wt%, the preparation efficiency is lower; while the saturation solubility of acrylonitrile in the electrolyte was 7wt%. Therefore, the acrylonitrile content is preferably 4 to 7wt%.
The invention also provides a method for preparing adiponitrile by electrolyzing acrylonitrile, which adopts the electrolyte to carry out electrolytic reaction.
In an alternative embodiment, the cathode of the electrolytic reaction is Cd or Pb or alloy thereof, and the anode is carbon steel or stainless steel or PbO 2 。
In an alternative embodiment, the reaction temperature of the electrolysis reaction is 30-70 ℃ and the current density is 200-5000A/m 2 . The current density is less than 200A/m 2 The production efficiency is too low, and more electrolytic tanks are required to be invested to achieve the same productionEnergy is available; the current density is greater than 5000A/m 2 The amount of generated current is large, and side reactions are increased.
After the electrolytic reaction is finished, the electrolytic solution is mixed with crude adiponitrile to absorb unreacted acrylonitrile, the mixture is subjected to oil-water separation to obtain an oil phase and a water phase containing acrylonitrile, adiponitrile and organic byproducts, and the oil phase is distilled to obtain acrylonitrile, crude adiponitrile and organic byproducts.
The invention is further described below by means of specific examples. These examples are merely exemplary and are not intended to limit the scope of the present invention in any way. In the following examples and comparative examples, reagents, materials and instruments used, unless otherwise specified, were commercially available.
In the examples below, all reactions were carried out in an electrolyzer with electrode dimensions 100mm by 200mm by 5mm, with anode and cathode facing in parallel and anode and cathode spacing of 3mm. The electrolyte is pumped and circulated, and the linear speed of the electrolyte in the electrolytic tank is 1m/s. And (3) introducing current according to the current density and the electrode area, calculating the reaction time according to the Faraday efficiency of 100%, and carrying out electrolytic reaction according to the calculated current and the calculated reaction time. After completion of the reaction, CH was used 2 Cl 2 The organic matter in the electrolyte is extracted and weighed, the organic matter composition is analyzed by chromatography, and the acrylonitrile conversion rate and adiponitrile selectivity are calculated. The pressures involved are gauge pressures. The test results are shown in Table 1.
The calculation modes of the test conditions and the results are as follows:
current = electrode area x current density;
reaction time= (2×acrylonitrile mass×faraday constant)/(molar mass of acrylonitrile×current);
acrylonitrile conversion= (1-mass of acrylonitrile remaining/mass of acrylonitrile added) ×100%;
adiponitrile yield = (mass of adiponitrile actually received/theoretical mass of complete conversion of acrylonitrile to adiponitrile) ×100%.
The compounds of formulas (a) to (F) described in examples and comparative examples are shown below:
example 1
The electrolyte used contained 3.5wt% EDTA sodium salt, 7wt% sodium dihydrogen phosphate, and 1.5wt% borax, 2.5wt% modified quaternary phosphonium salt C by adding H 3 PO 4 And NaOH to adjust the pH of the electrolyte to 8. The acrylonitrile concentration is 7wt%, the solution linear velocity is 1m/s, the cathode is Cd, and the anode is PbO 2 Current density 1000A/m 2 。
Example 2
The electrolyte used contained 3.5wt% EDTA sodium salt, 7wt% sodium dihydrogen phosphate, and 1.5wt% borax, 2.5wt% modified quaternary phosphonium salt D, by adding H 3 PO 4 And NaOH to adjust the pH of the electrolyte to 8. The acrylonitrile concentration is 7wt%, the solution linear velocity is 1m/s, the cathode is Cd, and the anode is PbO 2 Current density 1000A/m 2 。
Example 3
The electrolyte contains EDTA sodium salt 3wt%, sodium dihydrogen phosphate 7wt%, borax 0.5wt%, and modified quaternary phosphonium salt E0.5 wt%, by adding H 3 PO 4 And NaOH to adjust the pH of the electrolyte to 8. The acrylonitrile concentration is 7wt%, the solution linear velocity is 1.1m/s, the cathode is Cd, and the anode is PbO 2 Current density 1100A/m 2 。
Example 4
The electrolyte used contained 3wt% EDTA sodium salt, 7wt% sodium dihydrogen phosphate, and 0.5wt% borax, 5wt% modified quaternary phosphonium salt F by adding H 3 PO 4 And NaOH to adjust the pH of the electrolyte to 8. The acrylonitrile concentration is 7wt%, the solution linear velocity is 1.1m/s, the cathode is Cd, and the anode is PbO 2 Current density 1100A/m 2 。
Example 5
The electrolyte used contained 3wt% EDTA sodium salt, 7wt% sodium dihydrogen phosphate, and 0.5wt% borax, 5wt% modified quaternary phosphonium salt F by adding H 3 PO 4 And NaOH to adjust the pH of the electrolyte to 8. The acrylonitrile concentration is 7wt%, the solution linear velocity is 1.1m/s, the cathode is Cd, and the anode is PbO 2 Current density 1100A/m 2 。
Comparative example 1
The electrolyte contains EDTA potassium salt 3.5wt%, sodium dihydrogen phosphate 5wt%, borax 0.3wt%, and ionic liquid A2 wt%, and H is added 3 PO 4 And NaOH to adjust the pH of the electrolyte to 8. The acrylonitrile concentration is 7wt%, the solution linear velocity is 1.3m/s, the cathode is Cd, and the anode is PbO 2 Current density 1200A/m 2 。
Comparative example 2
The electrolyte contains EDTA sodium salt 4wt%, sodium dihydrogen phosphate 8wt%, borax 0.5wt%, and modified quaternary ammonium salt B2 wt%, by adding H 3 PO 4 And NaOH to adjust the pH of the electrolyte to 8. The acrylonitrile concentration is 7wt%, the solution linear velocity is 1.2m/s, the cathode is Cd, and the anode is PbO 2 Current density 1000A/m 2 。
TABLE 1
As can be seen from the results of Table 1, higher target product selectivity can be obtained using the quaternary phosphonium salt used in the present invention. This is of great importance for the economy of the process for dimerization of acrylonitrile to adiponitrile.
The preferred embodiments of the invention disclosed above are intended only to assist in the explanation of the invention. The preferred embodiments are not exhaustive or to limit the invention to the precise form disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best understand and utilize the invention. The invention is limited only by the claims and the full scope and equivalents thereof.
Claims (10)
1. The electrolyte for preparing adiponitrile from acrylonitrile by electrocatalytic reaction is characterized by comprising acrylonitrile, modified quaternary phosphonium salt and water, wherein the cation of the modified quaternary phosphonium salt is a group shown in a formula (a 1) or a formula (b 1) which is connected to one end of the structure in a formula (f), and the other end of the structure is connected to a group shown in a formula (a 1), (b 1), (c), (d) or (e);
wherein R is 2 ～R 22 Each independently is a C1-C5 alkyl group; n=1 to 6.
2. Electrolyte according to claim 1, characterized in that the content of the modified quaternary phosphonium salt in the electrolyte is 0.01-3 wt%, preferably 0.01-1 wt%.
3. The electrolyte of claim 1 wherein the anion of the modified quaternary phosphonium salt is one or more of hydroxide, bisulfate, sulfate, phosphate, hydrogen phosphate, dihydrogen phosphate, acetate, nitrate, bis (trifluoromethanesulfonyl) imide anions.
4. The electrolyte of claim 1, wherein the electrolyte further comprises 0.1 to 10wt% EDTA or sodium or potassium salts thereof, and 0.01 to 5wt% borax.
5. The electrolyte of claim 1, further comprising 1 to 20wt% of a phosphate salt, the phosphate salt being at least one of potassium phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, sodium phosphate, disodium hydrogen phosphate, and sodium dihydrogen phosphate.
6. Electrolyte according to claim 1, characterized in that the acrylonitrile content in the electrolyte is 4-7 wt%.
7. The process according to claim 1, wherein n is 4 to 6 and R 2 ～R 12 Each independently is a C2-C4 alkyl group.
8. A method for preparing adiponitrile by electrolyzing acrylonitrile, characterized in that the electrolytic reaction is performed by using the electrolyte as claimed in any one of claims 1 to 7.
9. The method according to claim 8, wherein the cathode of the electrolytic reaction is Cd or Pb or an alloy thereof, and the anode is carbon steel or stainless steel or PbO 2 。
10. The method according to claim 8, wherein the reaction temperature of the electrolytic reaction is 30 to 70 ℃ and the current density is 200 to 5000A/m 2 。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210102964.1A CN116555789A (en) | 2022-01-27 | 2022-01-27 | Electrolyte for preparing adiponitrile by electrocatalytic acrylonitrile and electrolysis method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210102964.1A CN116555789A (en) | 2022-01-27 | 2022-01-27 | Electrolyte for preparing adiponitrile by electrocatalytic acrylonitrile and electrolysis method |
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