CN113083319A - Method for preparing chloroethylene synthetic catalyst by extracting and separating manganese slag - Google Patents
Method for preparing chloroethylene synthetic catalyst by extracting and separating manganese slag Download PDFInfo
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- 239000002893 slag Substances 0.000 title claims abstract description 59
- 239000003054 catalyst Substances 0.000 title claims abstract description 45
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical group ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title claims abstract description 42
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000011572 manganese Substances 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 40
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 39
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 41
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 32
- 239000000284 extract Substances 0.000 claims abstract description 31
- 238000003756 stirring Methods 0.000 claims abstract description 31
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 20
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 claims abstract description 20
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 20
- 239000010941 cobalt Substances 0.000 claims abstract description 20
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 20
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 20
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 19
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052802 copper Inorganic materials 0.000 claims abstract description 19
- 239000010949 copper Substances 0.000 claims abstract description 19
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 19
- 239000011701 zinc Substances 0.000 claims abstract description 19
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 18
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims abstract description 17
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 16
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 230000001105 regulatory effect Effects 0.000 claims abstract description 15
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims abstract description 10
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims abstract description 10
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims abstract description 10
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims abstract description 10
- 239000011565 manganese chloride Substances 0.000 claims abstract description 10
- 235000002867 manganese chloride Nutrition 0.000 claims abstract description 10
- 229940099607 manganese chloride Drugs 0.000 claims abstract description 10
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims abstract description 10
- 239000011592 zinc chloride Substances 0.000 claims abstract description 10
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 10
- 238000000746 purification Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 238000000605 extraction Methods 0.000 abstract description 14
- 239000006228 supernatant Substances 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 239000012043 crude product Substances 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 9
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000004064 recycling Methods 0.000 description 3
- 239000005997 Calcium carbide Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 229960002523 mercuric chloride Drugs 0.000 description 2
- LWJROJCJINYWOX-UHFFFAOYSA-L mercury dichloride Chemical compound Cl[Hg]Cl LWJROJCJINYWOX-UHFFFAOYSA-L 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 125000000101 thioether group Chemical group 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- RCTYPNKXASFOBE-UHFFFAOYSA-M chloromercury Chemical compound [Hg]Cl RCTYPNKXASFOBE-UHFFFAOYSA-M 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000007038 hydrochlorination reaction Methods 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/07—Preparation of halogenated hydrocarbons by addition of hydrogen halides
- C07C17/08—Preparation of halogenated hydrocarbons by addition of hydrogen halides to unsaturated hydrocarbons
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a method for preparing a chloroethylene synthetic catalyst by extracting and separating manganese slag, which comprises the following steps: stirring the sulfide slag and dilute hydrochloric acid, introducing chlorine gas for extraction, taking supernatant, adding calcium carbonate powder to remove sulfate ions, and obtaining extract. Analyzing the contents of zinc chloride, manganese chloride, copper chloride, cadmium chloride, nickel chloride and cobalt chloride in the extract, adding a regulator according to the weight, and regulating the ratio of zinc, manganese, copper, cadmium, nickel and cobalt in the extract to be 2-5: 1-3: 0.1-1 to obtain a regulating solution. Then adding active carbon to soak and dry to prepare the catalyst. The catalyst prepared by the test is used for producing chloroethylene, the reaction temperature is 110-; the purity of the chloroethylene crude product after rectification reaches 99.99V/%. Can meet the production requirement of chloroethylene.
Description
Technical Field
The invention relates to the technical field of manganese slag recycling, in particular to a method for preparing a chloroethylene synthetic catalyst by extracting and separating valuable elements from sulfide slag generated in the manganese electrolyte purification process.
Background
China is the biggest world for manganese production, consumption and export, and the capacity is over 200 million tons/year, which accounts for about 98% of the total global manganese production. The industrial manganese slag refers to filtered acid slag (about 90 percent of the total slag) in the production of electrolytic manganese metal, electrolytic manganese dioxide and industrial manganese sulfate, and sulfide slag (about 10 percent of the total slag) generated in the solution purification process, and the annual output is about 1800 ten thousand tons. At present, mixed stockpiling treatment is mainly adopted, which causes serious influence on the ecological environment. The manganese slag treatment and the resource economic and effective recovery of valuable elements are always a worldwide problem.
Disclosure of Invention
The invention aims to provide a method for preparing a chloroethylene synthetic catalyst by extracting and separating manganese slag. The catalyst for synthesizing chloroethylene is prepared by separating valuable metal elements in the sulfide slag. The production cost is low. The comprehensive recovery and high-value utilization of the manganese slag are realized.
The technical scheme of the invention is as follows:
a method for preparing a chloroethylene synthetic catalyst by extracting and separating manganese slag is used for extracting and separating valuable metal elements from sulfide slag generated in the purification process of manganese electrolyte to prepare the chloroethylene synthetic catalyst, and comprises the following steps:
s1, mixing the sulfide slag with dilute hydrochloric acid, introducing chlorine gas, stirring and extracting, taking supernate, adding calcium carbonate powder to remove sulfate ions, and obtaining extract liquor;
s2, analyzing the contents of zinc chloride, manganese chloride, copper chloride, cadmium chloride, nickel chloride and cobalt chloride in the extract, adding a regulator by weight, and regulating the ratio of zinc, manganese, copper, cadmium, nickel and cobalt in the extract to be 2-7: 1-4: 0.1-2 to obtain a regulated solution;
and S3, adding activated carbon into the adjusted solution, soaking and drying to obtain the catalyst.
In the method for preparing the chloroethylene synthetic catalyst by extracting and separating the manganese slag, in the step s1, the sulfide slag and the dilute hydrochloric acid are added into a stirring tank, chlorine is introduced into the stirring tank at the temperature of between 40 and 70 ℃ to react for 20 to 120 minutes under stirring, and the supernatant is taken and added with calcium carbonate powder to remove sulfate ions, so that the extract is obtained.
In the method for preparing the chloroethylene synthetic catalyst by extracting and separating the manganese slag, in the step s1, the sulfide slag and the dilute hydrochloric acid are added into a stirring tank, chlorine is introduced into the stirring tank at the temperature of between 50 and 60 ℃ to react for 40 to 100 minutes under stirring, and the supernatant is taken and added with calcium carbonate powder to remove sulfate ions, so that the extract is obtained.
In the method for preparing the chloroethylene synthetic catalyst by extracting and separating the manganese slag, the regulator is zinc chloride, manganese chloride, copper chloride, cadmium chloride, nickel chloride and cobalt chloride.
In the method for preparing the chloroethylene synthetic catalyst by extracting and separating the manganese slag, the step s2 is used for adjusting the proportion of zinc, manganese, copper, cadmium, nickel and cobalt in the solution to be 3-5: 2-3: 0.1-1.
In the method for preparing the chloroethylene synthetic catalyst by extracting and separating the manganese slag, the ratio of zinc, manganese, copper, cadmium, nickel and cobalt in the solution is adjusted to be 5: 3: 1.
Has the advantages that:
chloroethylene is a monomer of polyvinyl chloride (PVC) which is one of five synthetic resins in the world, and is mainly produced by a calcium carbide acetylene method and a petroleum ethylene method. The existence of energy sources rich in coal, lean oil and little gas in China determines that the calcium carbide acetylene method will continue to be the main process for producing vinyl chloride in China in a long time in the future, namely mercury chloride catalyzes the reaction of acetylene and hydrogen chloride to generate vinyl chloride. However, the highly toxic mercuric chloride catalyst seriously pollutes the environment and harms human health, so that the development of a new high-efficiency catalyst is needed to replace the traditional mercuric chloride catalyst.
The average grade of associated trace nickel and cobalt elements in manganese ore in China is 50ppm to 100 ppm. The grade is extremely low, the reserves are huge, and the enrichment and recovery are extremely difficult, so that the method is always regarded as a resource which is temporarily difficult to utilize. In the production of electrolytic manganese, nickel and cobalt elements enter the sulfide slag in the processes of sulfurization, purification and purification of leachate. The sulfide slag contains elements such as manganese, nickel and cobalt, as well as zinc, copper, cadmium and the like, but the content is not high, and the cost is difficult to reduce by the conventional single metal recovery method.
The earlier research of the applicant finds that the sulfide slag generated in the solution purification process of the existing electrolytic manganese process contains: 10-15% of Mn; 5-8% of Zn; 1 to 1.5 percent of Ni; co 01-0.5%; h2About 30 percent of O, and trace heavy metal elements such as copper, chromium, cadmium and the like and other impurities. Can be used for preparing multi-metal composite catalyst for synthesizing chloroethylene reaction catalyst. The manganese slag and dilute hydrochloric acid are mixed and stirred, chlorine gas is introduced for extraction to obtain the metal ion chlorinated complex salt extract, a regulator is added according to the content of each ion in the extract, the proportion of zinc, manganese, copper, cadmium, nickel and cobalt in the extract is regulated, and activated carbon is added for impregnation to prepare the chloroethylene synthetic catalyst.
To further prove the catalytic effect of the catalyst prepared by the invention, the inventors prepared the catalyst for vinyl chloride synthesis by using the adjustment solution prepared from the manganese slag extract according to the process of the embodiment 1-3, and carried out the test using the TDCH-20170123 type acetylene hydrochlorination fixed bed reaction device manufactured by tianjin Tiandi Chuanzhi scientific and technological development ltd, and the results were as follows:
TABLE 1 test results of vinyl chloride Synthesis test
Through analysis of a table 1 chloroethylene synthesis test, the chloroethylene synthesis catalyst prepared by extracting and separating valuable elements from manganese slag is used, when chloroethylene is synthesized, the reaction temperature is 110-; the purity of the chloroethylene crude product after rectification reaches 99.99V/%. Can meet the production requirement of chloroethylene.
The technical scheme of the invention provides a process method for preparing the chloroethylene catalyst by treating the manganese slag, extracting and separating valuable elements and recycling resources, and a catalyst proportion with high catalytic efficiency, so that the comprehensive recycling of metal elements in the manganese slag is realized, and the economic benefit is obvious.
The specific implementation mode is as follows:
the present invention is further illustrated by the following examples, which are not to be construed as limiting the invention. The structures or processes not specifically mentioned are conventional in the art.
Example (b): the method for preparing the chloroethylene synthetic catalyst by extracting and separating manganese slag extracts and separates valuable metal elements from sulfide slag generated in the purification process of manganese electrolyte to prepare the chloroethylene synthetic catalyst, and comprises the following steps:
s1, mixing the sulfide slag with dilute hydrochloric acid, introducing chlorine gas, stirring and extracting, taking supernate, adding calcium carbonate powder to remove sulfate ions, and obtaining extract liquor;
s2, analyzing the contents of zinc chloride, manganese chloride, copper chloride, cadmium chloride, nickel chloride and cobalt chloride in the extract, adding a regulator by weight, and regulating the ratio of zinc, manganese, copper, cadmium, nickel and cobalt in the extract to be 2-7: 1-4: 0.1-2 to obtain a regulated solution;
and S3, adding activated carbon into the adjusted solution, soaking and drying to obtain the catalyst.
And step s1, adding the sulfide slag and dilute hydrochloric acid into a stirring tank, introducing chlorine gas at 40-70 ℃, stirring for reaction for 20-120 minutes, taking supernate, adding calcium carbonate powder to remove sulfate ions, and obtaining extract.
And step s1, adding the sulfide slag and dilute hydrochloric acid into a stirring tank, introducing chlorine gas at 50-60 ℃, stirring for reaction for 40-100 minutes, taking supernate, adding calcium carbonate powder to remove sulfate ions, and obtaining extract.
The regulator is zinc chloride, manganese chloride, copper chloride, cadmium chloride, nickel chloride and cobalt chloride.
More preferably, the step s2 adjusts the ratio of zinc, manganese, copper, cadmium, nickel and cobalt in the solution to 3-5: 2-3: 0.1-1.
More preferably, the ratio of zinc, manganese, copper, cadmium, nickel and cobalt in the conditioning solution is 5: 3: 1.
The following examples are provided in connection with the specific cases:
example 1. A method for preparing a chloroethylene synthetic catalyst by extracting and separating manganese slag comprises the following steps:
s1, stirring the sulfide slag and dilute hydrochloric acid, introducing chlorine gas for extraction, taking supernatant, adding calcium carbonate powder to remove sulfate ions, and obtaining extract.
S2, after the extraction liquid is filtered and separated, the content of zinc, manganese, copper, cadmium, nickel and cobalt in the extraction liquid is analyzed, and a regulator is added according to the weight, and the ratio of the zinc, the manganese, the copper, the cadmium, the nickel and the cobalt in the extraction liquid is regulated to be 2: 5: 3: 0.1, so that a regulated solution is obtained.
And S3, adding activated carbon into the adjusted solution, soaking and drying to obtain the catalyst.
In the step s1, the sulfide slag and the dilute hydrochloric acid are added into a stirring tank, chlorine gas is introduced into the stirring tank at 40 ℃ to react for 120 minutes, supernatant is taken, and calcium carbonate powder is added to remove sulfate ions, so that extract liquor is obtained.
The step s1 can also be adding the sulfide residue and dilute hydrochloric acid into a stirring tank, introducing chlorine gas at 50 ℃, stirring for reaction for 100 minutes, taking the supernatant, adding calcium carbonate powder, and removing sulfate ions to obtain the extract.
The regulator is zinc chloride, manganese chloride, copper chloride, cadmium chloride, nickel chloride and cobalt chloride.
Example 2. A method for preparing a chloroethylene synthetic catalyst by extracting and separating manganese slag comprises the following steps:
s1, stirring the sulfide slag and dilute hydrochloric acid, introducing chlorine gas for extraction, and taking extract liquor;
s2, after the extraction liquid is filtered and separated, the content of zinc, manganese, copper, cadmium, nickel and cobalt in the extraction liquid is analyzed, and a regulator is added according to the weight, and the ratio of the zinc, the manganese, the copper, the cadmium, the nickel and the cobalt in the extraction liquid is regulated to be 5: 2: 1: 0.5, so that a regulated solution is obtained.
And S3, adding activated carbon into the adjusted solution, soaking and drying to obtain the catalyst.
And step s1, adding the sulfide slag and dilute hydrochloric acid into a stirring tank, introducing chlorine gas at 70 ℃, stirring for reacting for 80 minutes, taking supernatant, adding calcium carbonate powder, and removing sulfate ions to obtain extract.
The step s1 can also be adding the sulfide residue and dilute hydrochloric acid into a stirring tank, introducing chlorine gas at 55 ℃, stirring for reaction for 90 minutes, taking the supernatant, adding calcium carbonate powder to remove sulfate ions, and obtaining the extract.
The method for preparing the chloroethylene synthetic catalyst by extracting and separating the manganese slag comprises the step of preparing a catalyst by using a manganese slag extracting and separating method, wherein the regulator is zinc chloride, manganese chloride, copper chloride, cadmium chloride, nickel chloride and cobalt chloride.
Example 3. A method for preparing a chloroethylene synthetic catalyst by extracting and separating manganese slag comprises the following steps:
s1, stirring the sulfide slag and dilute hydrochloric acid, introducing chlorine gas for extraction, and taking extract liquor;
s2, after the extraction liquid is filtered and separated, the content of zinc, manganese, copper, cadmium, nickel and cobalt in the extraction liquid is analyzed, and a regulator is added according to the weight, and the ratio of the zinc, the manganese, the copper, the cadmium, the nickel and the cobalt in the extraction liquid is regulated to be 3.5: 4: 2: 1, so that a regulated solution is obtained.
And S3, adding activated carbon into the adjusted solution, soaking and drying to obtain the catalyst.
In the step s1, the sulfide slag and the dilute hydrochloric acid are added into a stirring tank, chlorine gas is introduced into the stirring tank at 60 ℃ to react for 40 minutes, supernatant is taken, and calcium carbonate powder is added to remove sulfate ions, so that extract liquor is obtained.
The regulator is zinc chloride, manganese chloride, copper chloride, cadmium chloride, nickel chloride and cobalt chloride.
Claims (6)
1. A method for preparing a chloroethylene synthetic catalyst by extracting and separating manganese slag is characterized by comprising the following steps: extracting and separating valuable metal elements from sulfide slag generated in the purification process of manganese electrolyte to prepare the chloroethylene synthetic catalyst, and comprises the following steps:
s1, mixing the sulfide slag with dilute hydrochloric acid, introducing chlorine gas, stirring and extracting, taking supernate, adding calcium carbonate powder to remove sulfate ions, and obtaining extract liquor;
s2, analyzing the contents of zinc chloride, manganese chloride, copper chloride, cadmium chloride, nickel chloride and cobalt chloride in the extract, adding a regulator by weight, and regulating the ratio of zinc, manganese, copper, cadmium, nickel and cobalt in the extract to be 2-7: 1-4: 0.1-2 to obtain a regulated solution;
and S3, adding activated carbon into the adjusted solution, soaking and drying to obtain the catalyst.
2. The method for preparing vinyl chloride synthetic catalyst by extracting and separating manganese slag according to claim 1, wherein the method comprises the following steps: and step s1, adding the sulfide slag and dilute hydrochloric acid into a stirring tank, introducing chlorine gas at 40-70 ℃, stirring for reaction for 20-120 minutes, taking supernate, adding calcium carbonate powder to remove sulfate ions, and obtaining extract.
3. The method for preparing vinyl chloride synthetic catalyst by extracting and separating manganese slag according to claim 2, wherein the method comprises the following steps: and step s1, adding the sulfide slag and dilute hydrochloric acid into a stirring tank, introducing chlorine gas at 50-60 ℃, stirring for reaction for 40-100 minutes, taking supernate, adding calcium carbonate powder to remove sulfate ions, and obtaining extract.
4. The method for preparing vinyl chloride synthetic catalyst by extracting and separating manganese slag according to claim 1, wherein the method comprises the following steps: the regulator is zinc chloride, manganese chloride, copper chloride, cadmium chloride, nickel chloride and cobalt chloride.
5. The method for preparing vinyl chloride synthetic catalyst by extracting and separating manganese slag according to claim 1, wherein the method comprises the following steps: the step s2 is to adjust the ratio of zinc, manganese, copper, cadmium, nickel and cobalt in the solution to 3-5: 2-3: 0.1-1.
6. The method for preparing vinyl chloride synthetic catalyst by extracting and separating manganese slag according to claim 5, wherein the method comprises the following steps: the ratio of zinc, manganese, copper, cadmium, nickel and cobalt in the solution is adjusted to be 5: 3: 1.
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Citations (5)
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|---|---|---|---|---|
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