CN116855968A - Method and device for producing L-cysteine by aid of mediator-assisted electrochemical decomposition and hydrogen sulfide coupling - Google Patents
Method and device for producing L-cysteine by aid of mediator-assisted electrochemical decomposition and hydrogen sulfide coupling Download PDFInfo
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- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 229910000037 hydrogen sulfide Inorganic materials 0.000 title claims abstract description 95
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 title claims abstract description 56
- 239000004201 L-cysteine Substances 0.000 title claims abstract description 28
- 235000013878 L-cysteine Nutrition 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 24
- 238000000354 decomposition reaction Methods 0.000 title claims abstract description 21
- 230000008878 coupling Effects 0.000 title claims abstract description 17
- 238000010168 coupling process Methods 0.000 title claims abstract description 17
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 17
- LEVWYRKDKASIDU-QWWZWVQMSA-N D-cystine Chemical compound OC(=O)[C@H](N)CSSC[C@@H](N)C(O)=O LEVWYRKDKASIDU-QWWZWVQMSA-N 0.000 claims abstract description 41
- 229960003067 cystine Drugs 0.000 claims abstract description 41
- 239000003792 electrolyte Substances 0.000 claims abstract description 27
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 19
- 230000003647 oxidation Effects 0.000 claims abstract description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000007789 gas Substances 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 7
- PWKSKIMOESPYIA-UHFFFAOYSA-N 2-acetamido-3-sulfanylpropanoic acid Chemical compound CC(=O)NC(CS)C(O)=O PWKSKIMOESPYIA-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000003487 electrochemical reaction Methods 0.000 claims description 39
- 238000010521 absorption reaction Methods 0.000 claims description 32
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 14
- 239000011148 porous material Substances 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000012528 membrane Substances 0.000 claims description 9
- 239000003115 supporting electrolyte Substances 0.000 claims description 9
- 239000000956 alloy Substances 0.000 claims description 8
- 229910045601 alloy Inorganic materials 0.000 claims description 8
- 239000000919 ceramic Substances 0.000 claims description 8
- 239000006004 Quartz sand Substances 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 101150071746 Pbsn gene Proteins 0.000 claims description 6
- 229920000557 Nafion® Polymers 0.000 claims description 5
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims description 5
- LBUJPTNKIBCYBY-UHFFFAOYSA-N 1,2,3,4-tetrahydroquinoline Chemical compound C1=CC=C2CCCNC2=C1 LBUJPTNKIBCYBY-UHFFFAOYSA-N 0.000 claims description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 4
- 239000002041 carbon nanotube Substances 0.000 claims description 4
- 239000007809 chemical reaction catalyst Substances 0.000 claims description 4
- 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
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 238000007743 anodising Methods 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052745 lead Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 abstract description 12
- 229910052717 sulfur Inorganic materials 0.000 abstract description 12
- 238000004064 recycling Methods 0.000 abstract description 8
- 239000002699 waste material Substances 0.000 abstract description 7
- 239000003638 chemical reducing agent Substances 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 abstract 1
- 231100000614 poison Toxicity 0.000 abstract 1
- 239000003440 toxic substance Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 28
- 230000008569 process Effects 0.000 description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 238000006722 reduction reaction Methods 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 8
- 230000009467 reduction Effects 0.000 description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 229910020658 PbSn Inorganic materials 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical group [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- KIUMMUBSPKGMOY-UHFFFAOYSA-N 3,3'-Dithiobis(6-nitrobenzoic acid) Chemical compound C1=C([N+]([O-])=O)C(C(=O)O)=CC(SSC=2C=C(C(=CC=2)[N+]([O-])=O)C(O)=O)=C1 KIUMMUBSPKGMOY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 238000005303 weighing Methods 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
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/02—Preparation of sulfur; Purification
- C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
-
- 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
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
-
- 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
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/50—Processes
-
- 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
- C25B3/25—Reduction
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention discloses a method and a device for producing L-cysteine by coupling hydrogen sulfide through electrochemical decomposition assisted by a mediator, wherein the method comprises the following steps: reducing the solution containing cystine in an electrochemical cathode to obtain L-cysteine, and carrying out electrochemical anodic oxidation on the solution containing reduced mediator to obtain mediator oxidized electrolyte; contacting the mediator oxidation state electrolyte with a gas containing hydrogen sulfide to obtain a mixture of sulfur, protons and a reduced state mediator; wherein the mixture containing protons and a reducing agent is returned to the electrochemical anode for recycling. The method converts cystine and hydrogen sulfide into L-cysteine and sulfur by means of electrochemical technology, and realizes recycling of waste and toxic substances.
Description
Technical Field
The invention relates to a method and a device for producing L-cysteine by coupling hydrogen sulfide through electrochemical decomposition assisted by a mediator, belonging to the field of waste recycling.
Background
Hydrogen sulfide is a harmful gas which exists in a large amount in coalbed methane, shale gas and natural gas and is generated in chemical processes such as petroleum refining, natural gas processing and the like. Currently, the Claus (Claus) process is mainly used in industry to solve the problem of hydrogen sulfide. The specific principle is as follows:
H 2 S+3/2O 2 →SO 2 +H 2 O (1)
2H 2 S+SO 2 →2H 2 O+3/xS x (2)
conventional claus processes may partially oxidize hydrogen sulfide to produce water and sulfur. Although this process can effectively recover sulfur in hydrogen sulfide, hydrogen contained in hydrogen sulfide is oxidized into water to be wasted. The inventor of the earlier-stage patent proposes a method (CN 107815698B) for preparing sulfur and hydrogen by assisting the total decomposition of hydrogen sulfide by a medium, and effectively solves the problem that hydrogen in the hydrogen sulfide in the traditional Claus process is wasted. However, in the chemical industry, the further utilization of the generated hydrogen still requires a great deal of energy consumption, and the inflammable and explosive nature of the hydrogen brings serious challenges to the transportation and storage of the hydrogen. Therefore, the development of a new process that directly achieves the effective utilization of protons in the process of hydrogen sulfide decomposition has important practical significance.
L-cysteine is an important industrial raw material and is widely applied to the fields of medicines, cosmetics, foods and the like. Currently, electrochemical methods are widely used in industry because of their ability to produce high purity L-cysteine. In the operation process of the electrochemical method, the cathode reduces cystine to generate L-cysteine, the anodic oxidation water generates oxygen and protons, and the protons provide a hydrogen source for the cathode reduction of cystine. However, the anode product has slower dynamic characteristics in the process of generation, greatly increases energy consumption, and has lower industrial added value.
Disclosure of Invention
In order to solve the technical problems, the method couples the decomposition of the hydrogen sulfide with the reduction of the cystine, can simultaneously convert the hydrogen sulfide and the cystine into products with high added value, reduces the cystine into L-cysteine and converts the hydrogen sulfide into sulfur, thereby not only effectively solving the problem of hydrogen waste in the hydrogen sulfide, but also overcoming the problem of high energy consumption of the reduction of the cystine.
In order to achieve the above object, the technical scheme of the present invention is as follows:
in one aspect, the invention provides a method for producing L-cysteine by coupling hydrogen sulfide through mediator-assisted electrochemical decomposition, comprising the following steps:
reducing the solution containing cystine in the cathode of an electrochemical reaction tank to obtain L-cysteine, and anodizing the solution containing reduced mediator in the electrochemical reaction tank to obtain mediator oxidized electrolyte;
the mediator oxidation state electrolyte is contacted with a gas containing hydrogen sulfide to obtain a mixture of elemental sulfur, protons and a reduced state mediator;
wherein, the mixture containing proton and reduced state medium is returned to the anode of the electrochemical reaction tank for circulation.
Preferably, the mediator is selected from Ce 3+ /Ce 4+ ，VO 2+ /VO 2 + ，I-/I 3 - ，Fe 2+ /Fe 3+ At least one of tetrahydroquinoline/quinoline, phosphomolybdic acid/sodium phosphomolybdate; the molar concentration of the medium is 0.1-3 mol/L.
Preferably, the electrochemical reaction catalyst of the electrochemical reaction cell cathode comprises at least one of a metal Pb, cu, ag, sn, ti and an alloy PbCu, pbAg, pbSn, cuAg, snAg thereof;
the electrochemical reaction catalyst of the electrochemical reaction tank anode comprises at least one of Ti, activated carbon, graphite, graphene and carbon nano tubes.
Preferably, the supporting electrolyte in the electrochemical reaction cell is independently selected from HNO 3 、H 2 SO 4 、HCl、HClO 4 At least one of (a) and (b);
the molar concentration of the supporting electrolyte is 1 multiplied by 10 -3 ～10mol/L。
Preferably, the concentration of cystine at the cathode of the electrochemical reaction tank is 0.01-1.5 mol/L.
Preferably, the volume concentration of the hydrogen sulfide in the gas containing the hydrogen sulfide is 5-100%.
Preferably, the voltage applied between the anode and the cathode of the electrochemical reaction cell is 0.5-5V.
Preferably, the voltage is a direct current voltage.
In another aspect, the invention provides an apparatus for use in the above method comprising an electrochemical reaction cell and H 2 S absorption tower;
the electrochemical reaction tank comprises an anode chamber and a cathode chamber, and the anode chamber and the cathode chamber are separated by a diaphragm; the liquid outlet of the anode chamber is connected with the liquid inlet pipeline of the hydrogen sulfide absorption tower; the liquid inlet of the anode chamber is connected with the liquid outlet pipeline of the hydrogen sulfide absorption tower.
Preferably, the membrane is a Nafion membrane or a porous ceramic membrane, and the pores of the membrane are 0.1-300 microns.
Preferably, a plurality of layers of sieve plates are arranged in the hydrogen sulfide absorption tower at intervals along the longitudinal direction; the sieve plate is a quartz sand sieve plate, and the pore diameter of the quartz sand sieve plate is 50-450 micrometers.
The invention relates to a method and a device for producing L-cysteine by coupling hydrogen sulfide through electrochemical decomposition assisted by a mediator. In the present invention, the process of converting cystine and hydrogen sulfide into high value added products is performed in two steps. The first step is completed in an electrochemical reaction tank, and an anode chamber and a cathode chamber of the electrochemical reaction tank are isolated by a diaphragm; cystine is converted into L-cysteine through electrocatalytic reduction reaction carried out at a cathode, and a mediator oxidation state electrolyte is obtained at an anode. The second step is carried out in an absorption tower, the medium oxidation state electrolyte is conveyed to a hydrogen sulfide absorption tower by a pump to react with hydrogen sulfide to obtain sulfur and protons, the sulfur is separated and recovered, and the protons and the reduced medium are conveyed to an anode of an electrochemical reaction tank by the pump to complete circulation.
In the present invention, the "anode of electrochemical reaction cell":the anode chamber of the electrochemical reaction cell "refers to an anode region including an electrolysis means, an electrolyte contained in the anode region, and an anode inserted into the electrolyte. "electrochemical reaction cell cathode" and "electrochemical reaction cell cathode chamber" refer to a cathode region comprising an electrolysis device, an electrolyte contained within the cathode region, and a cathode inserted into the electrolyte. "reduced state mediator" and "oxidized state mediator" refer to the reduced and oxidized states of the mediator, respectively, such as mediator Fe 2+ /Fe 3+ ，Fe 2+ Is a 'reduced state mediator', fe 3+ Is an "oxidation state mediator". The "mediator oxidation state electrolyte" and "mediator reduction state electrolyte" refer to electrolytes containing an oxidation state mediator and a reduction state mediator, respectively.
The beneficial effects of the invention are as follows:
(1) According to the method for producing L-cysteine by coupling hydrogen sulfide through electrochemical decomposition assisted by a mediator, provided by the invention, cystine is reduced to L-cysteine at a cathode, an oxidized mediator electrolyte is produced at an anode, and the obtained oxidized mediator electrolyte is used for oxidizing hydrogen sulfide to form sulfur, so that the recycling and recovery of cystine and hydrogen sulfide are realized at the same time, the problem of hydrogen waste in hydrogen sulfide is effectively solved, and the problem of high energy consumption in cystine reduction is overcome.
(2) The method of the invention has the advantages that the conversion rate of the hydrogen sulfide is not lower than 80 percent and the conversion rate of the cystine is not lower than 85 percent through the high oxidation rate of the mediator to the hydrogen sulfide.
(3) The device for producing L-cysteine by coupling the hydrogen sulfide through the electrochemical decomposition assisted by the mediator comprises an electrochemical reaction tank and a hydrogen sulfide absorption tower which are circularly used in series, wherein the electrochemical reaction tank and the hydrogen sulfide absorption tower are connected through a liquid path, so that synchronous recycling of hydrogen sulfide-containing gas and cystine solution and closed cycle recycling of anolyte are realized, and the treatment efficiency is improved.
(4) According to the invention, the reduction of cystine to L-cysteine can be realized through one set of device, and meanwhile, the oxidization of hydrogen sulfide to sulfur is realized, so that the recovery and reutilization of waste are realized.
Drawings
FIG. 1 is a schematic illustration of the process of the invention in which mediator-assisted electrochemical decomposition of hydrogen sulfide is coupled to produce L-cysteine;
FIG. 2 is a schematic diagram of a device for producing L-cysteine by coupling hydrogen sulfide through mediator-assisted electrochemical decomposition;
in the figure: 100. an electrochemical reaction tank 200 and a hydrogen sulfide absorption tower.
Detailed Description
The present invention is described in detail below with reference to examples, but the present invention is not limited to these examples.
The starting materials and catalysts in the examples of the present invention were purchased commercially, unless otherwise specified.
Example 1 electrochemical co-conversion of cystine and Hydrogen sulfide
Referring to fig. 1, the electrolysis is performed in an electrochemical reaction cell in this embodiment; the absorption of hydrogen sulfide is performed in a hydrogen sulfide absorption column. A cathode chamber and an anode chamber are arranged in the electrochemical reaction tank, the cathode chamber and the anode chamber are separated by a Nafion diaphragm, and the diaphragm pore is 1 micron; 4 layers of quartz sand sieve plates are arranged in the hydrogen sulfide absorption tower at intervals along the longitudinal direction of the hydrogen sulfide absorption tower, and the pore space of the sieve plates is 50 microns.
Adding HCl (1 mol/L) solution containing 0.5mol/L cystine into a cathode chamber to serve as a cathode electrolyte; the anode chamber is added with FeCl containing 1.5mol/L 2 Is used as an anolyte solution; one end of the cathode is inserted into the catholyte, and one end of the anode is inserted into the anolyte; the longitudinal cross-sectional dimensions of the cathode and anode were rectangular with dimensions of 2cm by 4 cm.
The cathode catalyst is PbSn alloy, the electrode substrate is a commercially available carbon sheet, and the cathode catalyst is loaded on the carbon sheet to prepare a cathode electrode; the anode is an activated carbon modified commercial carbon sheet; the external constant voltage source is respectively connected with the cathode and the anode through leads, and meanwhile, the ammeter is connected in series into the circuit, and in the embodiment, the reaction constant voltage source applies 1.5V direct current voltage, and after the voltage is applied, the current of the reaction system is observed to be 320mA.
After the reaction starts, the color of the anode solution is gradually deepened, and after 50 hours of reaction, the mediator oxidation state electrolyte FeCl is obtained 3 Oxidizing medium to form electrolyte FeCl 3 Introducing into hydrogen sulfide absorption tower, pumping into anode chamber 1.5mol/L FeCl 2 The HCl (1 mol/L) solution of (B) is continuously reacted; the cystine-containing solution is reduced in the cathodic compartment to give L-cysteine.
Mixing the mixed gas (Ar: H) 2 S=90%: 10%, V/V) is slowly introduced into the hydrogen sulfide absorption tower, the gas flow rate is 25ml/min, light yellow sediment is separated out from the hydrogen sulfide absorption tower along with the reaction, and the liquid flowing out from the liquid outlet of the hydrogen sulfide absorption tower is introduced into the anode chamber to be used as anode electrolyte for recycling.
Determining the molar mass of the generated L-cysteine by using an Ellman reagent colorimetric method, wherein the molar mass of the cystine is 168mmol, the molar mass of the generated L-cysteine is 299mmol, and the conversion efficiency of the cystine is 89%; and collecting sediment in the hydrogen sulfide absorption tower, centrifugally separating out sulfur, weighing 9.6g after drying, and introducing 334.8mmol of hydrogen sulfide in the whole reaction process to obtain 298.5mmol of elemental sulfur, wherein the conversion rate of the hydrogen sulfide is 89%.
Example 2 electrochemical co-conversion of cystine and Hydrogen sulfide
The difference from example 1 is that:
the diaphragm of the electrolytic cell is a porous ceramic diaphragm, and the pore size of the diaphragm is 0.1 micron; the cathode catalyst is metallic lead, the anode catalyst is metallic Ti, and 0.1mol/L Ce 2 (SO 4 ) 3 H of (2) 2 SO 4 The (0.5 mol/L) solution is an anolyte, and the oxidation state Ce contained in the mediator oxidation state electrolyte obtained by the anode 2 (SO 4 ) 3 Namely Ce (SO) 4 ) 2 。
The conversion of hydrogen sulfide was 88% and the conversion of cystine was 94% as measured in example 2.
Example 3 electrochemical co-conversion of cystine and Hydrogen sulfide
The difference from example 1 is that:
the cathode catalyst is PbCu alloy, and the anode is a carbon sheet modified by a carbon nano tube; HNO in 1.5mol/L phosphomolybdic acid 3 (0.001 mol/L) solution and 1.5mol/L sodium nitrate as anolyte, and oxygen as mediator obtained by anodeThe electrolyte in the chemical state contains sodium phosphomolybdate which is phosphomolybdic acid in the oxidation state; mixed gas H 2 The S volume fraction was 30%.
The hydrogen sulfide conversion was 83% and the cystine conversion was 90% as measured in example 3.
Example 4 electrochemical co-conversion of cystine and Hydrogen sulfide
The difference from example 1 is that:
the concentration of the anode medium is 3mol/L, and the concentration of the anode supporting electrolyte is 10mol/L H 2 SO 4 Solution, cathode supporting electrolyte is 10mol/L H 2 SO 4 A solution; the concentration of cystine is 1.5mol/L, and the volume fraction of hydrogen sulfide is 100%; the voltage applied between the anode and the cathode was 5V; the pore of the porous ceramic membrane is 300 microns; the pores of the quartz sand screen were 450 microns.
The hydrogen sulfide conversion was 81% and the cystine conversion was 85% as measured in example 4.
Example 5 electrochemical co-conversion of cystine and Hydrogen sulfide
The difference from example 1 is that:
the concentration of the anode mediator is 0.1mol/L, and the concentration of the anode supporting electrolyte is 0.5mol/L H 2 SO 4 Solution, cathode supporting electrolyte is H of 0.5mol/L 2 SO 4 A solution; cystine concentration is 0.01mol/L, and hydrogen sulfide volume fraction is 5%; the voltage applied between the anode and the cathode was 2.0V; the pore space of the porous ceramic diaphragm is 0.01 micron; the pores of the quartz sand screen were 100 microns.
The hydrogen sulfide conversion was 85% and the cystine conversion was 90% as measured in example 5.
Example 6
Referring to fig. 2, the apparatus includes: an electrochemical reaction cell 100 and a hydrogen sulfide absorption tower 200; the electrochemical reaction cell 100 comprises an anode chamber and a cathode chamber, wherein the anode chamber generates a mediator oxidation state electrolyte, and the cathode chamber carries out catalytic reduction on cystine; the anode chamber is connected with a liquid inlet pipeline of the hydrogen sulfide absorption tower 200, the mediator oxidation state electrolyte enters the hydrogen sulfide absorption tower through a pump, passes through the hydrogen sulfide absorption tower 200 from top to bottom, meets the gas to be treated in the hydrogen sulfide absorption tower 200 for reaction, and sulfur simple substances formed after the hydrogen sulfide in the gas is oxidized are collected and recovered by a sieve plate in the hydrogen sulfide absorption tower 200; the bottom of the hydrogen sulfide absorption tower 200 is provided with an air inlet, the top of the air inlet is provided with an air outlet, and the gas to be treated enters the absorption device 200 from the air inlet and moves upwards to pass through the multi-layer sieve plate and then leaves from the air outlet; the mixture of protons and the reduced-state mediator leaves at the bottom liquid outlet of the hydrogen sulfide absorption tower 200, and then enters the anode chamber through a pump to be recycled as electrolyte. The yield of waste gas and waste liquid in the whole treatment process is low, the treatment of the cystine and hydrogen sulfide-containing gas can be realized only by using the electrochemical reaction tank 100 and the hydrogen sulfide absorption tower 200 in a connecting way, the equipment is simple, the cost is low, and the treatment efficiency is high.
The parameters used in examples 1 to 5 are listed in Table 1. The results obtained in examples 1 to 5 are shown in Table 2.
TABLE 1 parameters used in examples 1-5
| Examples numbering | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 |
| Anode medium | FeCl 2 | Ce 2 (SO 4 ) 3 | Phosphomolybdic acid | FeCl 2 | FeCl 2 |
| Anode mediator concentration | 1.5mol/L | 0.1mol/L | 1.5mol/L | 3mol/L | 0.1mol/L |
| Anode catalyst | Activated carbon | Metal Ti | Carbon nanotubes | Activated carbon | Activated carbon |
| Cathode catalyst | PbSn alloy | Metallic lead | PbCu alloy | PbSn alloy | PbSn alloy |
| Cystine concentration | 0.5mol/L | 0.5mol/L | 0.5mol/L | 1.5mol/L | 0.01mol/L |
| Supporting electrolyte | HCl | H 2 SO 4 | HNO 3 | H 2 SO 4 | H 2 SO 4 |
| Supporting electrolyte concentration | 1mol/L | 0.5mol/L | 0.001 mol/L | 10mol/L | 0.5mol/L |
| Applying a voltage | 1.5V | 1.5V | 1.5V | 5V | 2V |
| Diaphragm | Nafion diaphragm | Porous ceramic | Nafion diaphragm | Porous ceramic | Porous ceramic |
| Diaphragm aperture | 1 micron | 0.1 micron | 1 micron | 300 micrometers | 0.01 micron |
| Pore of sieve plate | 50 micrometers | 50 micrometers | 50 micrometers | 450 micrometers | 100 micrometers |
| Hydrogen sulfide volume ratio | 10％ | 10％ | 30％ | 100％ | 5％ |
Table 2 results obtained by treating the conversion efficiencies of hydrogen sulfide and cystine in examples 1 to 5
Wherein, the conversion rate of the hydrogen sulfide is as follows:
the cystine conversion rate is as follows:and (5) calculating.
As can be seen from examples 1 to 5 above, by adopting the method provided by the invention, a large amount of mediator is produced by adopting the anolyte capable of realizing the conversion of the oxidation state and the reduction state, so that hydrogen sulfide and cystine are respectively converted into elemental sulfur and L-cysteine, and the recycling of wastes is realized. The yield of the obtained product is higher, and the value of the product is higher.
While the invention has been described in terms of preferred embodiments, it will be understood by those skilled in the art that various changes and modifications can be made without departing from the scope of the invention, and it is intended that the invention is not limited to the specific embodiments disclosed.
Claims (10)
1. A method for producing L-cysteine by coupling hydrogen sulfide through mediator-assisted electrochemical decomposition, which is characterized by comprising the following steps:
reducing the solution containing cystine in the cathode of an electrochemical reaction tank to obtain L-cysteine, and anodizing the solution containing reduced mediator in the electrochemical reaction tank to obtain mediator oxidized electrolyte;
the mediator oxidation state electrolyte is contacted with a gas containing hydrogen sulfide to obtain a mixture of elemental sulfur, protons and a reduced state mediator;
wherein, the mixture containing proton and reduced state medium is returned to the anode of the electrochemical reaction tank for circulation.
2. The method for producing L-cysteine by coupling hydrogen sulfide through electrochemical decomposition with assistance of a mediator according to claim 1, wherein the mediator is selected from the group consisting of Ce 3+ /Ce 4+ ，VO 2+ /VO 2 + ，I-/I 3 - ，Fe 2+ /Fe 3+ At least one of tetrahydroquinoline/quinoline, phosphomolybdic acid/sodium phosphomolybdate;
the molar concentration of the medium is 0.1-3 mol/L.
3. The method for producing L-cysteine by coupling hydrogen sulfide through mediator-assisted electrochemical decomposition according to claim 1, wherein the electrochemical reaction catalyst of the electrochemical reaction cell cathode comprises at least one of a metal Pb, cu, ag, sn, ti and an alloy PbCu, pbAg, pbSn, cuAg, snAg thereof;
the electrochemical reaction catalyst of the electrochemical reaction tank anode comprises at least one of Ti, activated carbon, graphite, graphene and carbon nano tubes.
4. The method for producing L-cysteine by coupling hydrogen sulfide through mediator-assisted electrochemical decomposition of claim 1 wherein said electrochemical reaction cell supports an electrolyte independently selected from the group consisting of HNO 3 、H 2 SO 4 、HCl、HClO 4 At least one of (a) and (b);
the molar concentration of the supporting electrolyte is 1 multiplied by 10 -3 ～10mol/L。
5. The method for producing L-cysteine by coupling hydrogen sulfide through electrochemical decomposition assisted by a mediator as claimed in claim 1, wherein the concentration of cystine at the cathode of the electrochemical reaction tank is 0.01-1.5 mol/L.
6. The method for producing L-cysteine by coupling hydrogen sulfide through electrochemical decomposition with the aid of a mediator according to claim 1, wherein the volume concentration of hydrogen sulfide in the hydrogen sulfide-containing gas is 5% -100%.
7. The method for producing L-cysteine by coupling hydrogen sulfide through mediator-assisted electrochemical decomposition according to claim 1, wherein a voltage of 0.5 to 5V is applied between an anode and a cathode of the electrochemical reaction cell.
8. An apparatus for a method of producing L-cysteine by coupling a mediator-assisted electrochemical decomposition of hydrogen sulfide according to any of claims 1 to 7, comprising an electrochemical reaction cell and a hydrogen sulfide absorption column;
the electrochemical reaction tank comprises an anode chamber and a cathode chamber, and the anode chamber and the cathode chamber are separated by a diaphragm; the liquid outlet of the anode chamber is connected with the liquid inlet pipeline of the hydrogen sulfide absorption tower; the liquid inlet of the anode chamber is connected with the liquid outlet pipeline of the hydrogen sulfide absorption tower.
9. The device of claim 8, wherein the membrane is a Nafion membrane or a porous ceramic membrane, and the membrane has pores of 0.1 to 300 microns.
10. The apparatus according to claim 8, wherein a plurality of layers of sieve plates are longitudinally spaced apart in the hydrogen sulfide absorption tower; the sieve plate is a quartz sand sieve plate, and the pore diameter of the quartz sand sieve plate is 50-450 micrometers.
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