CN117263229A - Method for preparing refined cuprous chloride from liquid-phase DMC catalyst waste mud - Google Patents
Method for preparing refined cuprous chloride from liquid-phase DMC catalyst waste mud Download PDFInfo
- Publication number
- CN117263229A CN117263229A CN202311395266.6A CN202311395266A CN117263229A CN 117263229 A CN117263229 A CN 117263229A CN 202311395266 A CN202311395266 A CN 202311395266A CN 117263229 A CN117263229 A CN 117263229A
- Authority
- CN
- China
- Prior art keywords
- liquid
- mixture
- cuprous chloride
- solid
- waste mud
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910021591 Copper(I) chloride Inorganic materials 0.000 title claims abstract description 50
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 title claims abstract description 50
- 229940045803 cuprous chloride Drugs 0.000 title claims abstract description 50
- 239000003054 catalyst Substances 0.000 title claims abstract description 39
- 239000002699 waste material Substances 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 32
- 239000007791 liquid phase Substances 0.000 title claims abstract description 21
- 239000007788 liquid Substances 0.000 claims abstract description 59
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 37
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000007787 solid Substances 0.000 claims abstract description 20
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000460 chlorine Substances 0.000 claims abstract description 16
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 16
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 15
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 230000000873 masking effect Effects 0.000 claims abstract description 10
- 238000000926 separation method Methods 0.000 claims abstract description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 64
- 239000000203 mixture Substances 0.000 claims description 36
- 238000003756 stirring Methods 0.000 claims description 33
- 238000001914 filtration Methods 0.000 claims description 20
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 16
- 238000010521 absorption reaction Methods 0.000 claims description 13
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N 4-methylimidazole Chemical compound CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims description 4
- 239000003814 drug Substances 0.000 claims description 4
- 238000007873 sieving Methods 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 239000010802 sludge Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 238000005832 oxidative carbonylation reaction Methods 0.000 claims description 2
- 238000001694 spray drying Methods 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims 2
- 238000005469 granulation Methods 0.000 claims 1
- 230000003179 granulation Effects 0.000 claims 1
- 238000004321 preservation Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 19
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 18
- 238000004458 analytical method Methods 0.000 description 16
- 239000000706 filtrate Substances 0.000 description 16
- 239000010949 copper Substances 0.000 description 14
- 238000005303 weighing Methods 0.000 description 13
- 239000012065 filter cake Substances 0.000 description 12
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 11
- 229910052802 copper Inorganic materials 0.000 description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 9
- 229960003280 cupric chloride Drugs 0.000 description 9
- 210000003298 dental enamel Anatomy 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 238000003921 particle size analysis Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000012047 saturated solution Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- -1 iron ions Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 229910009116 xCuO Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/04—Halides
- C01G3/05—Chlorides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a method for preparing refined cuprous chloride from catalyst waste mud filtered by a liquid-phase DMC device, which comprises the following steps: slowly adding catalyst waste mud into an ammonium chloride solution, adding a masking agent to adjust the pH value, carrying out solid-liquid separation, adding ammonia water into the liquid to adjust the pH value, carrying out solid-liquid separation again, obtaining a solid part, adding hydrochloric acid, adding hydroxylamine hydrochloride, heating under the protection of nitrogen, introducing chlorine into the solid part, continuously reacting for 2-5 h, isolating air, and drying to obtain a cuprous chloride product. The method changes waste into valuable, has low production cost, high product purity, short process flow, safety and environmental protection.
Description
Technical Field
The invention belongs to the technical field of chemical engineering, and particularly relates to a method for preparing refined cuprous chloride from liquid-phase DMC catalyst waste sludge.
Background
DMC (dimethyl carbonate) is prepared by using methanol, carbon monoxide and oxygen as raw materials, DMC and water are generated from the product, the main components of the catalyst are copper-based complex, the reaction equation is shown as follows, and the technology can be used at present
In order to realize homogeneous liquid phase circulation reaction, or single kettle intermittent reaction, complexing agent decomposition is caused by byproduct generation in the reaction process, so that copper ions lose protection, meanwhile, the existence of system product water can cause copper ion hydrolysis, basic cupric chloride, cupric hydroxide and cupric salt precipitate formed by the complexing agent after decomposition are generated, a small amount of precipitates of iron, calcium, silicon, sulfur and other ions are mixed in equipment corrosion, and the precipitates or insoluble matters can be filtered out through a filtering system in a production device, or catalyst waste mud is obtained by intermittent kettle cleaning, so that the catalyst active components of the system are lost, the catalytic activity is reduced, the productivity is reduced, meanwhile, in order to restore the catalytic activity of the system, the economic cost of enterprises is increased, one set of liquid phase DMC devices producing 10 ten thousand tons per year is increased, and the catalyst waste mud produced per year is about 100-300 tons, and is neither economical nor environment-friendly if the catalyst waste mud is directly abandoned.
The copper source of the copper-based complex catalyst for general liquid-phase DMC synthesis is cuprous chloride, the cuprous chloride is white tetrahedral crystal, the melted cuprous chloride is iron gray, and the cuprous chloride crystal is easily oxidized in air and water to generate basic cupric chloride (CuCl) in the storage process 2 ·xCuO·4H 2 O), even after the sealing treatment, is extremely easily oxidized for a long time, resulting in a decrease in the purity of cuprous chloride. Meanwhile, due to the complexity of a copper source, more impurity ions can be introduced into the copper source with low purity in the preparation process, and the catalytic activity of the prepared copper-based complex catalyst is reduced and even the catalytic activity of the catalyst is completely lost due to poisoning, so that the copper-based complex catalyst must use refined cuprous chloride meeting national standard as the copper source.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for preparing refined cuprous chloride from catalyst waste mud filtered by a liquid-phase DMC device.
The invention is realized by the following technical scheme:
a method for preparing refined cuprous chloride from liquid phase DMC catalyst waste mud, comprising the following steps:
step 1, slowly adding catalyst waste mud into an ammonium chloride solution in a stirring state to obtain a first mixture, and regulating the pH value of the first mixture to 1.5-2; stirring for 30-60 min, then carrying out solid-liquid separation to obtain a solid part as a first solid, and obtaining a liquid part as a first liquid to enter the step 2;
the catalyst waste mud is generated in the DMC process of the methanol liquid phase oxidative carbonylation method;
the mass ratio of the catalyst waste mud to the ammonium chloride solution is 1 (1-2);
step 2, adding a masking agent into the first liquid obtained in the step 1 to adjust the pH value to 7.1-7.5, stirring for 1-2 h to obtain a second mixture, carrying out solid-liquid separation on the second mixture to obtain a solid part which is a second solid, and obtaining a liquid part which is a second liquid, and entering the step 3; the masking agent is mainly used for removing impurity ions such as iron ions in copper;
the masking agent is a mixture prepared from triethanolamine and imidazole medicaments according to a molar ratio of 1:1;
step 3, adding ammonia water into the second liquid obtained in the step 2 to adjust the pH value to be 13-14, stirring for 1-2 h to obtain a third mixture, and carrying out solid-liquid separation on the third mixture to obtain a third solid as a solid part and a third liquid as a liquid part;
step 4, adding hydrochloric acid into the third solid obtained in the step 3 and stirring for 1-2 h to obtain a fourth mixture;
the adding amount of hydrochloric acid is 2-4 times of the mass of the third solid;
step 5, adding hydroxylamine hydrochloride into the fourth mixture, heating to 80-100 ℃ under the protection of nitrogen, and continuously stirring for 2-5 h to obtain a fifth mixture;
the adding amount of hydroxylamine hydrochloride is 1 to 1.5 times of the mass of the third solid;
step 6, heating the fifth mixture to 150-300 ℃, introducing chlorine into the fifth mixture, and continuously reacting for 2-5 h to obtain a sixth mixture after the reaction is finished;
the partial pressure of chlorine in the reaction system is 0.3-1 MPa,
and 7, isolating the sixth mixture from air and drying to obtain a cuprous chloride product.
In the above technical scheme, in the step 1, the ammonium chloride solution is a saturated ammonium chloride solution.
In the above technical scheme, in the step 1, the mass ratio of the catalyst waste mud to the ammonium chloride solution is 1:2.
In the above technical solution, in the step 1, the method for adjusting the pH of the first mixture is to add one or more of dilute hydrochloric acid, dilute acetic acid or dilute citric acid, preferably dilute hydrochloric acid, to the first mixture; further, the acid concentration is 0.1-1mol/L.
In the above technical scheme, in the step 2, the masking agent is a solution of a mixture prepared by triethanolamine and imidazole medicaments according to a molar ratio of 1:1, and the concentration of the masking agent is 0.1-1mol/L.
In the above technical scheme, in the step 2, the imidazole medicament is one or more of benzimidazole, N-methylimidazole and 4-methylimidazole.
In the above technical scheme, in the step 3, the concentration of the ammonia water is 20-30wt%.
In the above technical scheme, in the step 3, the obtained third liquid is recovered to prepare an ammonium chloride solution.
In the above technical scheme, the solid-liquid separation process is performed in a filtration mode.
In the above technical scheme, in the step 4, the concentration of the hydrochloric acid is 1-6 mol/L.
In the above technical scheme, in the step 5, the oxygen content is lower than 0.01vol% under the protection of nitrogen.
In the above technical scheme, in step 6, the reaction tail gas is absorbed by an absorption liquid, the absorption liquid is deionized water, the absorption liquid after the absorption is recovered for preparing hydrochloric acid solution, the atmosphere after the reaction is replaced by nitrogen after the reaction is completed, and the gas replaced after the reaction is absorbed by the absorption liquid.
In the technical scheme, in the step 6, the introduced chlorine is high-purity chlorine with the purity of 99.99vol%.
In the above technical scheme, in step 7, the dried cuprous chloride powder is obtained by spray drying the sixth mixture in the air-isolated state, and the dried cuprous chloride powder is granulated, sieved and stored in a dark place.
In the technical scheme, the steps 1 to 6 are all carried out in an enamel reactor.
The invention has the advantages and beneficial effects that:
1. the process recycles the catalyst waste mud filtered by the liquid phase DMC device to prepare refined cuprous chloride, and changes waste into valuables, wherein the utilization rate of the catalyst waste mud is higher than 95%; 2. compared with the expensive price of the high-purity reagent in the prior art, the catalyst waste mud belongs to waste and has low cost as a raw material; 3. compared with the prior art, the technology has the advantages that the metal ion types in the raw materials are complex, the product purity is high and the cuprous chloride content is higher than 99% by adding the masking agent, so that the national standard HG/T2960-2010 regulation is achieved; 4. the process flow is more reasonable, tail gas and tail liquid can be reused, and the process is safe and environment-friendly.
Drawings
FIG. 1 is a comparison of the FTIR spectrum of the refined cuprous chloride obtained in example 1 with a standard spectrum library;
FIG. 2 is an SEM image of the refined cuprous chloride obtained in example 1;
FIG. 3 shows the elemental analysis results of the purified cuprous chloride obtained in example 1;
FIG. 4 is a XRD spectrum of the refined cuprous chloride obtained in example 1 and a standard card comparison;
FIG. 5 is a graph showing the particle size analysis of the purified cuprous chloride obtained in example 1;
FIG. 6 is a weight loss curve of the purified cuprous chloride obtained in example 1 under air and nitrogen atmosphere;
FIG. 7 is a graph showing the specific surface area of purified cuprous chloride obtained in example 1;
FIG. 8 shows the physical adsorption curve of the purified cuprous chloride obtained in example 1.
Other relevant drawings may be made by those of ordinary skill in the art from the above figures without undue burden.
Detailed Description
In order to make the person skilled in the art better understand the solution of the present invention, the following describes the solution of the present invention with reference to specific embodiments.
Example 1:
step 1, adding 200g of saturated ammonium chloride solution into an enamel reaction kettle, starting stirring, slowly adding 100g of catalyst waste mud into the reaction kettle, slowly adding 0.1mol/L dilute hydrochloric acid into the kettle to adjust the pH of the kettle liquid to 1.5, continuously stirring for 30min, filtering the kettle liquid to obtain filtrate 1, drying filter residue 1, weighing the filter residue, and obtaining the filtrate with the mass of 2.562g.
And 2, returning the filtrate 1 to the reaction kettle, starting stirring, adding 0.1mol/L triethanolamine and benzimidazole mixed solution (the mol ratio of the triethanolamine to the benzimidazole is 1:1) into the kettle, regulating the PH of the kettle solution to 7.1 by using the triethanolamine and benzimidazole mixed solution, stirring for 1h, filtering the kettle solution to obtain filtrate 2, filtering residues 2, drying the residues, weighing the residues, and weighing the residues with the mass of 0.039g.
And 3, returning the filtrate 2 to the reaction kettle, adding 20% ammonia water into the reaction kettle, adjusting the pH to 13, stirring for 1.5h, filtering the kettle liquid to obtain a filter cake, drying and weighing the filter cake, wherein the mass of the filter cake is 97.254g, and the filtrate 3 is used for preparing the ammonium chloride saturated solution in the step 1.
Step 4, putting 97.254g of filter cake into an enamel reaction kettle, adding 194.508g of 1mol/L hydrochloric acid into the reaction kettle, and stirring for 2 hours;
step 5, adding 100g of hydroxylamine hydrochloride into the reaction kettle, then using nitrogen to replace a system to ensure that the oxygen content in the reaction kettle is lower than 0.01%, heating the reaction kettle to 80 ℃, and preserving heat and stirring for 2 hours;
step 6, continuously heating the reaction kettle to 150 ℃, introducing high-purity chlorine to make the partial pressure of the chlorine be 1MPa, and continuously reacting for 2 hours, wherein tail gas at the outlet of the reaction kettle is absorbed by deionized water;
step 7, after the reaction is finished, the gas in the reaction kettle is replaced by nitrogen, and the solvent in the step 6 is still used for absorbing the gas in the process; the absorption liquid after the reaction can be repeatedly used for preparing the hydrochloric acid solution in the step 3.
And 8, discharging the kettle liquid in the reaction kettle into a spray dryer for drying (isolating air), granulating and sieving the dried cuprous chloride powder in an air-isolated granulator, and directly sealing the sieved cuprous chloride with a packaging bag with a black lining bag in a dark place, wherein the purity of the sieved cuprous chloride is 99.23%.
Example 2:
step 1, adding 500g of saturated ammonium chloride solution into an enamel reaction kettle, starting stirring, slowly adding 250g of catalyst waste mud into the reaction kettle, slowly adding 0.5mol/L dilute hydrochloric acid into the kettle to adjust the pH of the kettle liquid to 1.7, continuously stirring for 45min, filtering the kettle liquid to obtain filtrate 1, drying filter residue 1, weighing the filter residue, and weighing the filter residue to 7.253g.
And 2, returning the filtrate 1 to the reaction kettle, starting stirring, adding 0.5mol/L of a mixed solution of triethanolamine and N-methylimidazole (the mol ratio of the triethanolamine to the N-methylimidazole is 1:1) into the kettle, adjusting the pH of the kettle liquid to 7.3 by using the mixed solution, stirring for 1.5 hours, filtering the kettle liquid to obtain filtrate 2, filtering residues 2, drying the filtering residues, weighing the filtering residues, and obtaining the product with the mass of 1.257g.
And 3, returning the filtrate 2 to the reaction kettle, adding 25% ammonia water into the reaction kettle, adjusting the pH to 13.5, stirring for 1.5h, filtering the kettle liquid to obtain a filter cake, drying and weighing the filter cake, wherein the mass of the filter cake is 241.374g, and the filtrate 3 is used for preparing the ammonium chloride saturated solution in the step 1.
Step 4, putting 241.374g of filter cake into an enamel reaction kettle, adding 724.122g of 3mol/L hydrochloric acid into the reaction kettle, and stirring for 3.5h;
step 5, adding 301g hydroxylamine hydrochloride into the reaction kettle, then using nitrogen to replace a system to ensure that the oxygen content in the reaction kettle is lower than 0.01%, heating the reaction kettle to 90 ℃, and preserving heat and stirring for 3.5h;
step 6, continuously heating the reaction kettle to 225 ℃, introducing high-purity chlorine to make the partial pressure of the chlorine be 0.5MPa, and continuously reacting for 3.5 hours, wherein tail gas at the outlet of the reaction kettle is absorbed by deionized water;
step 7, after the reaction is finished, the gas in the reaction kettle is replaced by nitrogen, and the solvent in the step 6 is still used for absorbing the gas in the process; the absorption liquid after the reaction can be repeatedly used for preparing the hydrochloric acid solution in the step 3.
And 8, discharging the kettle liquid in the reaction kettle into a spray dryer for drying (isolating air), granulating and sieving the dried cuprous chloride powder in an air-isolated granulator, and directly sealing the sieved cuprous chloride with a packaging bag with a black lining bag in a dark place, wherein the purity of the sieved cuprous chloride is 99.38%.
Example 3:
step 1, adding 2000g of saturated ammonium chloride solution into an enamel reaction kettle, starting stirring, slowly adding 1000g of catalyst waste mud into the reaction kettle, slowly adding 1mol/L dilute hydrochloric acid into the kettle to adjust the pH of the kettle liquid to 2.0, continuously stirring for 60min, filtering the kettle liquid to obtain filtrate 1, filtering residues 1, drying the filtering residues, weighing the filtering residues, and weighing the filtering residues with the mass of 20.325g.
And 2, returning the filtrate 1 to the reaction kettle, starting stirring, adding a mixed solution of 1mol/L triethanolamine and 4-methylimidazole (the mol ratio of the triethanolamine to the 4-methylimidazole is 1:1) into the kettle, adjusting the PH of the kettle liquid to 7.5 by using the mixed solution, stirring for 2 hours, filtering the kettle liquid to obtain filtrate 2, drying filter residues 2, weighing the filter residues, and weighing the filter residues with the mass of 3.258g.
And 3, returning the filtrate 2 to the reaction kettle, adding 30% ammonia water into the reaction kettle, adjusting the pH to 14.0, stirring for 2 hours, filtering the kettle liquid to obtain a filter cake, drying and weighing the filter cake, wherein the mass of the filter cake is 975.351g, and the filtrate 3 are used for preparing the ammonium chloride saturated solution in the step 1.
Step 4, putting 975.351g of filter cake into an enamel reaction kettle, adding 3901.404g of 6mol/L hydrochloric acid into the reaction kettle, and stirring for 5 hours;
step 5, adding 1462g of hydroxylamine hydrochloride into the reaction kettle, then using a nitrogen substitution system to ensure that the oxygen content in the reaction kettle is lower than 0.01%, heating the reaction kettle to 100 ℃, and preserving heat and stirring for 5 hours;
step 6, continuously heating the reaction kettle to 300 ℃, introducing high-purity chlorine to make the partial pressure of the chlorine be 0.3MPa, and continuously reacting for 5 hours, wherein tail gas at the outlet of the reaction kettle is absorbed by deionized water;
step 7, after the reaction is finished, the gas in the reaction kettle is replaced by nitrogen, and the solvent in the step 3 is still used for absorbing the gas in the process; the absorption liquid after the reaction can be repeatedly used for preparing the hydrochloric acid solution in the step 3.
And 8, discharging the kettle liquid in the reaction kettle into a spray dryer for drying (isolating air), granulating and sieving the dried cuprous chloride powder in an air-isolated granulator, and directly sealing the sieved cuprous chloride with a packaging bag with a black lining bag in a dark place, wherein the purity of the sieved cuprous chloride is 99.51%.
To verify the purity of CuCl after the deteriorated cuprous chloride was refined by the refining process, characterization analysis was performed on the refined cuprous chloride finally obtained in example 1:
the content of CuCl which accords with the national standard HG/T2960-2010 is more than or equal to 99 percent, and the CuCl is 2 The content is less than or equal to 0.6 percent.
The analytical instrument used:
EDS energy spectrometer; XRD X-ray diffractometer; inductively coupled plasma emission spectrometer (ICP-OES); FTIR fourier transform infrared spectrometer; GC-2014C gas chromatograph; mastersizer 3000E laser particle sizer; ASAP2460 U.S. microphone Dual standing specific surface area and pore size analysis; karl fischer moisture analyzer; an ultraviolet spectrophotometer; HG/T-2960-2010 national standard analysis method.
The FTIR analysis results are shown in fig. 1, and the infrared spectrum analysis shows that the sample is mainly CuCl, and the comparison of the sample and the CuCl standard picture is basically consistent.
SEM images are shown in fig. 2, and sample element analysis results are shown in fig. 3; as shown by SEM pictures and element analysis results, the sample has high purity, and the main components are Cu and Cl.
XRD analysis results are shown in FIG. 4, and half-width data of the samples are shown in the following table 1; the sample shows a typical cuprous chloride crystal diffraction peak, and the average grain diameter of the crystal is about 61.5nm;
TABLE 1 half Peak Width data for samples
Remarks: hlk the crystal plane, FWHM the full width at half maximum,indicating that the grain size unit is angstrom, 1 angstrom=0.1 nm
The ICPOES analysis results of the samples are shown in the following Table 2, and the ICPOES analysis results show that the samples have higher purity, and the content of Al, fe, K, mg, na, si and other elements is less than 100ppm.
TABLE 2 ICPOES analysis results
Particle size analysis of the sample is shown in FIG. 5, and from the result of particle size analysis, the particle size of 95% of the sample is less than 66.5. Mu.m.
The thermogravimetric analysis of the sample is shown in fig. 6, and the weight loss curve of the sample under the air and nitrogen atmosphere can be obtained, the weight loss of the sample is less before 426 ℃, and the weight loss is increased after 426 ℃, because the CuCl melting point is 426 ℃, and the melted sample is taken away and lost by the protective gas, so that the cuprous chloride purity of the product is higher.
The specific surface area analysis of the sample is shown in fig. 7, and the physical adsorption analysis of the sample is shown in fig. 8; the specific surface area of the sample is 89.5332 +/-0.3675 m 2 /g。
The samples were subjected to moisture analysis using a karl fischer moisture meter, with a water content of 0.193wt%.
The sample is subjected to experimental result SO according to HG/T-2960-2010 national standard analysis method 4 2- 、NO 3 - The content is lower than 10ppm.
Cu is subjected to ultraviolet spectrophotometry 2+ Analysis of sample Cu 2+ According to the analysis of the standard series method for configuring Cu ions with different concentrations, the experimental result is calculated Cu 2+ The content was 0.477%.
The detection results are summarized as follows:
relational terms such as "first" and "second", and the like may be used solely to distinguish one element from another element having the same name, without necessarily requiring or implying any actual such relationship or order between such elements.
The foregoing has described exemplary embodiments of the invention, it being understood that any simple variations, modifications, or other equivalent arrangements which would not unduly obscure the invention may be made by those skilled in the art without departing from the spirit of the invention.
Claims (10)
1. A method for preparing refined cuprous chloride from liquid phase DMC catalyst waste mud, which is characterized by comprising the following steps:
step 1, slowly adding catalyst waste mud into an ammonium chloride solution in a stirring state to obtain a first mixture, and regulating the pH value of the first mixture to 1.5-2; stirring for 30-60 min, then carrying out solid-liquid separation to obtain a solid part as a first solid, and obtaining a liquid part as a first liquid to enter the step 2;
the catalyst waste mud is generated in the DMC process of the methanol liquid phase oxidative carbonylation method;
the mass ratio of the catalyst waste mud to the ammonium chloride solution is 1 (1-2);
step 2, adding a masking agent into the first liquid obtained in the step 1 to adjust the pH value to 7.1-7.5, stirring for 1-2 h to obtain a second mixture, carrying out solid-liquid separation on the second mixture to obtain a solid part which is a second solid, and obtaining a liquid part which is a second liquid, and entering the step 3;
the masking agent is a mixture prepared from triethanolamine and imidazole medicaments according to a molar ratio of 1:1;
step 3, adding ammonia water into the second liquid obtained in the step 2 to adjust the pH value to be 13-14, stirring for 1-2 h to obtain a third mixture, and carrying out solid-liquid separation on the third mixture to obtain a third solid as a solid part and a third liquid as a liquid part;
step 4, adding hydrochloric acid into the third solid obtained in the step 3 and stirring for 1-2 h to obtain a fourth mixture;
the adding amount of hydrochloric acid is 2-4 times of the mass of the third solid;
step 5, adding hydroxylamine hydrochloride into the fourth mixture, heating to 80-100 ℃ under the protection of nitrogen, and continuously stirring for 2-5 h to obtain a fifth mixture;
the adding amount of hydroxylamine hydrochloride is 1 to 1.5 times of the mass of the third solid;
step 6, heating the fifth mixture to 150-300 ℃, introducing chlorine into the fifth mixture, and continuously reacting for 2-5 h to obtain a sixth mixture after the reaction is finished;
the partial pressure of chlorine in the reaction system is 0.3-1 MPa,
and 7, isolating the sixth mixture from air and drying to obtain a cuprous chloride product.
2. The method for preparing refined cuprous chloride from liquid phase DMC catalyst waste mud as claimed in claim 1 wherein in step 1, ammonium chloride solution is saturated ammonium chloride solution; the mass ratio of the catalyst waste mud to the ammonium chloride solution is 1:2.
3. The method of preparing refined cuprous chloride from liquid phase DMC catalyst waste mud according to claim 1, wherein in step 1, the pH of the first mixture is adjusted by adding one or more of dilute hydrochloric acid, dilute acetic acid or dilute citric acid, preferably dilute hydrochloric acid, to the first mixture; further, the acid concentration is 0.1-1mol/L.
4. The method for preparing refined cuprous chloride from waste liquid of liquid phase DMC catalyst as claimed in claim 1, wherein in said step 2, said masking agent is a solution of a mixture of triethanolamine and imidazole agent prepared according to a molar ratio of 1:1, and its concentration is 0.1-1mol/L.
5. The method of claim 1, wherein in step 2, the imidazole-based reagent is one or more of benzimidazole, N-methylimidazole, and 4-methylimidazole.
6. The method for preparing refined cuprous chloride from liquid phase DMC catalyst waste mud as claimed in claim 1 wherein in said step 3, said ammonia water concentration is 20-30 wt%; and (5) recycling the obtained third liquid to prepare an ammonium chloride solution.
7. The method for preparing refined cuprous chloride from liquid phase DMC catalyst waste mud as claimed in claim 1, wherein said solid-liquid separation process is carried out by filtration.
8. The method for preparing refined cuprous chloride from waste sludge of liquid phase DMC catalyst as claimed in claim 1 wherein in said step 4, said hydrochloric acid concentration is 1-6 mol/L;
and 5, under the protection of nitrogen, the oxygen content is lower than 0.01vol%.
9. The method for preparing refined cuprous chloride from liquid phase DMC catalyst waste sludge according to claim 1, wherein in step 6, reaction tail gas is absorbed by an absorption liquid, the absorption liquid is deionized water, hydrochloric acid solution configuration is carried out by recycling the absorption liquid after the absorption, atmosphere after the reaction is replaced by nitrogen after the reaction is finished, and the gas replaced after the reaction is absorbed by the absorption liquid;
the introduced chlorine is high-purity chlorine with the purity of 99.99vol%.
10. The method for preparing refined cuprous chloride from waste liquid of liquid phase DMC catalyst as claimed in claim 1, wherein said step 7, the dried cuprous chloride powder is obtained by spray drying said sixth mixture in the air-isolated state, and the granulation, sieving and light-protected preservation are performed in the air-isolated state.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311395266.6A CN117263229A (en) | 2023-10-25 | 2023-10-25 | Method for preparing refined cuprous chloride from liquid-phase DMC catalyst waste mud |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311395266.6A CN117263229A (en) | 2023-10-25 | 2023-10-25 | Method for preparing refined cuprous chloride from liquid-phase DMC catalyst waste mud |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117263229A true CN117263229A (en) | 2023-12-22 |
Family
ID=89208092
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311395266.6A Pending CN117263229A (en) | 2023-10-25 | 2023-10-25 | Method for preparing refined cuprous chloride from liquid-phase DMC catalyst waste mud |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117263229A (en) |
-
2023
- 2023-10-25 CN CN202311395266.6A patent/CN117263229A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10777858B2 (en) | Methods for purifying and recycling lead from spent lead-acid batteries | |
| US4233274A (en) | Method of extracting and recovering mercury from gases | |
| FI67407C (en) | FRAMSTAELLNING AV YTTERST FINFOERDELAT KOBOLTPULVER AV EN UTSPAEDD LOESNING | |
| EP4140952A1 (en) | Method for producing lithium hydroxide | |
| JPS6241721A (en) | Method of recovering iron oxide | |
| JP2009228030A (en) | Method for recovering residual nickel in electroless plating waste solution | |
| CN110983059B (en) | Method for recovering copper and arsenic from copper smelting white smoke leachate and arsenic filter cake | |
| EP3421627A1 (en) | Method for recovering scandium | |
| CN117263229A (en) | Method for preparing refined cuprous chloride from liquid-phase DMC catalyst waste mud | |
| US4279869A (en) | Process for recovering concentrated, purified tungsten values from brine | |
| US2977185A (en) | Process for the recovery and separation of lithium and aluminum from lithium aluminate complex | |
| KR101404597B1 (en) | Nitrate reduction by maghemite supported Cu-Pd bimetallic catalyst | |
| CN106800303B (en) | Method for preparing potassium iodide by using microchannel reactor | |
| CA1227338A (en) | Production of fine spherical copper powder | |
| JPS6059974B2 (en) | Palladium recovery method | |
| JPS5924731B2 (en) | Method for removing and recovering uranium or/and thorium from a liquid containing uranium or/and thorium | |
| USH1311H (en) | Methanol synthesis process | |
| US5089452A (en) | Method for preparing catalyst precursor for methanol synthesis | |
| US12278352B2 (en) | Methods for purifying and recycling lead from spent lead-acid batteries | |
| CN116162067B (en) | Preparation method of prothioconazole | |
| CN113213537B (en) | A kind of method for separating and preparing vanadium trioxide from mixed solution of vanadium and chromium | |
| CN109289488B (en) | High temperature furnace chlorine, argon-containing tail gas treatment system | |
| CN1153219A (en) | Method for extraction of gold from coal-oil gold-carried aggregate (gold chamber) | |
| JPS6148506A (en) | Refining method of fine particle by gaseous phase process | |
| JP3327110B2 (en) | Method for producing scandium triflate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |