CN111001401B - Method for preparing anthraquinone degradation product regenerant by using waste argil as raw material, anthraquinone degradation product regenerant and application thereof - Google Patents
Method for preparing anthraquinone degradation product regenerant by using waste argil as raw material, anthraquinone degradation product regenerant and application thereof Download PDFInfo
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- 239000012492 regenerant Substances 0.000 title claims abstract description 74
- 150000004056 anthraquinones Chemical class 0.000 title claims abstract description 69
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 238000000034 method Methods 0.000 title claims abstract description 61
- 239000007857 degradation product Substances 0.000 title claims abstract description 59
- 239000002699 waste material Substances 0.000 title claims abstract description 47
- 239000002994 raw material Substances 0.000 title claims abstract description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 58
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 29
- 239000000463 material Substances 0.000 claims abstract description 20
- 239000007787 solid Substances 0.000 claims abstract description 20
- 239000002253 acid Substances 0.000 claims abstract description 17
- 238000001125 extrusion Methods 0.000 claims abstract description 14
- 239000003513 alkali Substances 0.000 claims abstract description 12
- 238000004898 kneading Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000004927 clay Substances 0.000 claims description 33
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 20
- 238000004061 bleaching Methods 0.000 claims description 15
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 10
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 10
- 239000000292 calcium oxide Substances 0.000 claims description 10
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 239000002585 base Substances 0.000 claims description 7
- -1 tert-amyl Chemical group 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 239000000395 magnesium oxide Substances 0.000 claims description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 241000219782 Sesbania Species 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000005984 hydrogenation reaction Methods 0.000 claims description 4
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 4
- 239000001095 magnesium carbonate Substances 0.000 claims description 4
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 4
- 239000005416 organic matter Substances 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 238000010298 pulverizing process Methods 0.000 claims description 4
- 238000007873 sieving Methods 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 229920000858 Cyclodextrin Polymers 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 229940031958 magnesium carbonate hydroxide Drugs 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 claims description 2
- 238000010304 firing Methods 0.000 claims 1
- 150000002894 organic compounds Chemical class 0.000 claims 1
- 238000012216 screening Methods 0.000 claims 1
- 230000008929 regeneration Effects 0.000 abstract description 10
- 238000011069 regeneration method Methods 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 7
- 238000002360 preparation method Methods 0.000 abstract description 7
- 239000002910 solid waste Substances 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 13
- 239000012224 working solution Substances 0.000 description 12
- 238000001035 drying Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 4
- AXHRXVXCOMMNLG-UHFFFAOYSA-N 1-hydroxy-10h-anthracen-9-one Chemical compound C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2O AXHRXVXCOMMNLG-UHFFFAOYSA-N 0.000 description 3
- RJGDLRCDCYRQOQ-UHFFFAOYSA-N anthrone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3CC2=C1 RJGDLRCDCYRQOQ-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 239000002920 hazardous waste Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- HSKPJQYAHCKJQC-UHFFFAOYSA-N 1-ethylanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2CC HSKPJQYAHCKJQC-UHFFFAOYSA-N 0.000 description 1
- QMEFGSMJWCNACE-UHFFFAOYSA-N 2-ethyl-1-hydroxy-10h-anthracen-9-one Chemical compound C1=CC=C2C(=O)C3=C(O)C(CC)=CC=C3CC2=C1 QMEFGSMJWCNACE-UHFFFAOYSA-N 0.000 description 1
- JHTIRPSWNPNDDC-UHFFFAOYSA-N 2-ethyl-10h-anthracen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC=C3CC2=C1 JHTIRPSWNPNDDC-UHFFFAOYSA-N 0.000 description 1
- SJEBAWHUJDUKQK-UHFFFAOYSA-N 2-ethylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC=C3C(=O)C2=C1 SJEBAWHUJDUKQK-UHFFFAOYSA-N 0.000 description 1
- PXLXSNXYTNRKFR-UHFFFAOYSA-N 6-ethyl-1,2,3,4-tetrahydroanthracene-9,10-dione Chemical compound O=C1C2=CC(CC)=CC=C2C(=O)C2=C1CCCC2 PXLXSNXYTNRKFR-UHFFFAOYSA-N 0.000 description 1
- IJUCUVQETSCNAL-UHFFFAOYSA-N C(C)C1CC=2C(C3=CC=CC=C3CC=2CC1)=O Chemical compound C(C)C1CC=2C(C3=CC=CC=C3CC=2CC1)=O IJUCUVQETSCNAL-UHFFFAOYSA-N 0.000 description 1
- NFIHRPFKFCOISK-UHFFFAOYSA-N CCC1CCC2=C(C1O)C(=O)C3=CC=CC=C3C2 Chemical compound CCC1CCC2=C(C1O)C(=O)C3=CC=CC=C3C2 NFIHRPFKFCOISK-UHFFFAOYSA-N 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000010977 unit operation Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/16—Clays or other mineral silicates
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/20—Regeneration or reactivation
-
- 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
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
-
- 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
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
- B01J23/04—Alkali metals
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/232—Carbonates
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
- C01B15/01—Hydrogen peroxide
- C01B15/022—Preparation from organic compounds
- C01B15/023—Preparation from organic compounds by the alkyl-anthraquinone process
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Detergent Compositions (AREA)
Abstract
The invention relates to the field of preparation of a hydrogen peroxide industrial regenerant by an anthraquinone process, and discloses a method for preparing an anthraquinone degradation product regenerant by taking waste argil as a raw material, the anthraquinone degradation product regenerant and application thereof. Wherein, the method comprises the following steps: (1) Mixing the waste argil, the extrusion aid, the first potassium carbonate and the solid alkali to obtain a first material; (2) Kneading the first material and acid to obtain a second material; (3) And extruding the second material into strips and roasting to obtain the anthraquinone degradation product regenerant. The method adopts the waste argil directly treated as solid waste as a raw material, realizes the reutilization of the waste argil, saves the cost, has good regeneration effect on anthraquinone degradation products by the prepared regenerant, and can obviously improve the increment of effective anthraquinone.
Description
Technical Field
The invention relates to the field of hydrogen peroxide industrial regenerants, in particular to a method for preparing an anthraquinone degradation product regenerant by using waste argil as a raw material, the anthraquinone degradation product regenerant and application thereof.
Background
The anthraquinone process is a process for industrially producing hydrogen peroxide in large quantities, in which anthraquinone as a carrier of cyclic hydrogenation is dissolved in a suitable organic solvent to form a working solution, and the hydrogen peroxide is produced by the technological operations of hydrogenation, oxidation, extraction, purification, post-treatment and the like. Due to many factors, anthraquinone can generate various side reactions to generate complex derivatives, which are collectively called degradation products, such as anthrone, hydroxy anthrone, tetrahydroanthraquinone epoxide, and the like, in the long-term recycling process. The formation of degradation products not only directly increases the consumption of anthraquinone, but also changes the physicochemical properties of the working fluid and, in severe cases, even affects the unit operation. Currently, clay (activated alumina) is commonly used to regenerate the degradation products, so as to achieve the purposes of maintaining the stable operation of the system and reducing the production cost. However, the clay widely used at present has low regeneration efficiency of degradation products, and the clay bed needs to be frequently replaced. The waste clay generated by replacing the clay bed in the hydrogen peroxide industry in China is up to tens of thousands of tons every year, and in addition, a large amount of working solution carried in the waste clay can pollute the environment. At present, almost all provinces manage the waste clay according to solid hazardous waste, the transportation and transfer procedures of the waste clay are complex, and the treatment cost is higher. Therefore, it is necessary to develop a method for recycling spent bleaching clay.
CN103879969A discloses a preparation method of a regenerant for preparing hydrogen peroxide by an anthraquinone process, wherein the method comprises the following steps: A. adding 1-10% nitric acid solution, glacial acetic acid or citric acid aqueous solution with volume percentage concentration of 1-65% into alumina powder, mixing well, and making into strip; B. drying in the shade at room temperature, and roasting at 600-900K for 3-5h to obtain a strip-shaped carrier; C. dissolving sodium hydroxide solid which is 1-6% of the total weight of the strip-shaped carrier in water to prepare a sodium hydroxide solution with the concentration of 0.1-5mol/L, soaking the strip-shaped carrier in the sodium hydroxide solution, taking out the strip-shaped carrier, and drying the strip-shaped carrier to obtain the sodium hydroxide carrier. However, in the preparation process, the process of impregnating NaOH without roasting is difficult to generate strong interaction between NaOH and alumina, and NaOH is easy to dissolve in trace moisture carried in the working solution, so that the NaOH is likely to be slowly lost in the long-term use process, and the subsequent hydrogenation process is easily adversely affected.
CN101376100A discloses a regeneration treatment method of activated alumina used in the regeneration process of hydrogen peroxide working solution. Wherein, the method comprises the following steps: the spent alumina discharged from a working solution regeneration bed in hydrogen peroxide production and combustion inert alumina enter a tower reactor from the upper part together, move downwards by means of gravity, oxygen-containing gas enters the reactor from the lower part of the tower reactor and moves upwards, the regenerated alumina and the combustion inert alumina after reaction are discharged from a discharging device at the bottom of the reactor, and the tail gas after reaction is discharged from a tail gas discharge port at the upper part of the reactor. However, the microstructure of the spent bleaching clay soaked in the working solution for a long time is changed, so that the activity is difficult to recover by simple roasting.
Therefore, the research and development of the anthraquinone degradation product regenerant prepared by taking the waste argil as the raw material have important significance.
Disclosure of Invention
The invention aims to solve the problems that the waste argil generated in the current hydrogen peroxide production process is solid hazardous waste and cannot be effectively reused, and provides a method for preparing an anthraquinone degradation product regenerant by using the waste argil as a raw material, the anthraquinone degradation product regenerant and application thereof. The method can take the waste argil directly treated as solid waste as a raw material, realizes the reutilization of the waste argil and saves the cost.
In order to achieve the above object, the present invention provides, in a first aspect, a method for preparing an anthraquinone degradation product regenerant, wherein the method comprises:
(1) Mixing the waste argil, the extrusion aid, the potassium carbonate and the solid alkali to obtain a first material;
(2) Kneading the first material and acid to obtain a second material;
(3) And extruding the second material into strips and roasting to obtain the anthraquinone degradation product regenerant.
The invention provides an anthraquinone degradation product regenerant prepared by the method.
The third aspect of the invention provides an application of the anthraquinone degradation product regenerant in a hydrogen peroxide production process.
Through the technical scheme, on one hand, the waste argil is used as a raw material, so that the problem of recycling the waste argil generated in the conventional hydrogen peroxide production process can be solved; in another aspect, the invention is made by introducing an acid, a first potassium carbonate, and a solid base during shaping; wherein, the addition of the acid not only can play a role of a binder, but also can react with alumina in the waste argil to reconstruct active sites; the introduction of the first potassium carbonate improves the regeneration performance of the regenerant on anthraquinone degradation products; the addition of the solid alkali introduces a new catalytic active component into the prepared regenerant, which is favorable for further improving the activity of the regenerant. The introduction of the first potassium carbonate and solid base is due to the fact that anthraquinone degrading species are abundant, and regeneration of the anthraquinone degrading species requires multiple catalytic active sites.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and these ranges or values should be understood to encompass values close to these ranges or values. For numerical ranges, each range between its endpoints and individual point values, and each individual point value can be combined with each other to give one or more new numerical ranges, and such numerical ranges should be construed as specifically disclosed herein.
The invention provides a preparation method of an anthraquinone degradation product regenerant, wherein the method comprises the following steps:
(1) Mixing the waste argil, the extrusion aid, the first potassium carbonate and the solid alkali to obtain a first material;
(2) Kneading the first material and acid to obtain a second material;
(3) And extruding the second material into strips and roasting to obtain the anthraquinone degradation product regenerant.
According to the invention, the waste argil is waste argil which is withdrawn from a post-treatment argil bed and a hydrogenated argil bed in the hydrogen peroxide production process and is in the form of pink or reddish brown globules, the average particle size of the waste argil is 2-6mm, and the specific surface area of the waste argil is 120-220m 2 Per g, pore volume of 0.20-0.30cm 3 (ii)/g; preferably, the spent bleaching earth has an average particle diameter of3-5mm, and the specific surface area is 150-200m 2 Per g, pore volume of 0.22-0.28cm 3 (ii)/g; in the invention, the adopted waste argil is the waste argil which is withdrawn from a post-treatment argil bed and a hydrogenated argil bed in the hydrogen peroxide production process, the average particle size is 4mm, and the specific surface area is 180m 2 Per g, pore volume of 0.26cm 3 /g。
Wherein, in the invention, the waste argil contains alumina, second potassium carbonate and organic matters; the second potassium carbonate is from a working solution with alkali in an alkali tower in the hydrogen peroxide preparation process, enters an after-treatment white clay bed and is adsorbed by white clay, and the organic matter is from the working solution adsorbed in the white clay using process. Preferably, the content of the alumina is 72 to 80 wt%, the content of the second potassium carbonate is 0.5 to 3 wt%, and the content of the organic matter is 17 to 27.5 wt% based on the total weight of the spent bleaching clay; in the present invention, it is preferable that the used waste clay contains alumina, second potassium carbonate, and an organic substance, and the content of the alumina is 74.9 wt%, the content of the second potassium carbonate is 1.6 wt%, and the content of the organic substance is 23.5 wt% based on the total weight of the waste clay. In the present invention, the organic matter refers to the working fluid entrained in the spent clay.
Preferably, the process further comprises pulverizing and sieving the spent bleaching earth to a powder having an average particle size of less than 120 μm, preferably 50-100 μm.
In the present invention, the spent bleaching earth needs to be subjected to pulverization and sieving treatment in advance, wherein the method of pulverization and sieving is not particularly limited as long as the spent bleaching earth can be pulverized and sieved to a powder having an average particle size of less than 120 μm, preferably 50 to 100 μm.
According to the invention, the extrusion aid is selected from one or more of sesbania powder, cyclodextrin and starch, and is preferably sesbania powder; in the invention, the extrusion aid is added to play a role in reducing extrusion pressure and is beneficial to extrusion into strips.
According to the invention, the solid base is selected from one or more of calcium oxide, magnesium oxide, calcium carbonate, magnesium carbonate and magnesium hydroxide; more preferably one or more of calcium oxide, magnesium oxide, calcium carbonate and magnesium carbonate. In the invention, the addition of the solid alkali can introduce a new catalytic active component into the regenerant prepared by the method, which is beneficial to improving the activity of the regenerant. According to the invention, relative to 100 parts by weight of the waste argil, the amount of the extrusion aid is 0.5-10 parts by weight, the amount of the solid alkali is 2-40 parts by weight, and the amount of the first potassium carbonate is 0.5-5 parts by weight; preferably, the extrusion aid is used in an amount of 1-5 parts by weight, the solid base is used in an amount of 4-20 parts by weight, and the first potassium carbonate is used in an amount of 1-3 parts by weight, relative to 100 parts by weight of the spent bleaching clay.
According to the invention, the acid is one or more of nitric acid, hydrochloric acid, oxalic acid, citric acid and trichloroacetic acid, preferably one or more of nitric acid, oxalic acid and citric acid; in the present invention, the concentration of the acid is 1 to 15% by weight, preferably 2 to 10% by weight; more preferably, the acid is used in an amount of 40 to 90 parts by weight, preferably 50 to 80 parts by weight, with respect to 100 parts by weight of the spent bleaching earth. In the present invention, the addition of the acid acts on the one hand as a binder and on the other hand is able to react with the alumina, so that the active sites are reconstituted.
According to the present invention, in the step (2), the kneading conditions include: the temperature is 20-50 deg.C, and the time is 10-60min.
According to the invention, the calcination is carried out in an air atmosphere with an air flow rate of 0.1-3L/100g, preferably 0.2-1.5L/100 g; in the present invention, it is to be noted that the air flow rate is measured with respect to the extruded strand precursor, that is, the air flow rate per hour is 0.1 to 3.0L, preferably 0.2 to 1.5L, based on 100g of the extruded strand precursor.
According to the invention, the roasting adopts a stage temperature rise mode:
the first stage is as follows: heating from room temperature to 100-300 ℃, wherein the heating rate is 1-20 ℃/min; preferably, the temperature is increased from room temperature to 120-250 ℃, wherein the temperature increase rate is 2-15 ℃/min;
and a second stage: preserving the heat for 1-6h at the temperature of 100-300 ℃; preferably, the temperature is kept for 2 to 4 hours at the temperature of 120 to 250 ℃;
and a third stage: heating from 100-300 ℃ to 450-750 ℃, wherein the heating rate is 1-15 ℃/min; preferably, the temperature is increased from 120-250 ℃ to 500-700 ℃, wherein the temperature increase rate is 2-10 ℃/min;
a fourth stage: preserving heat for 1-12h at the temperature of 450-750 ℃; preferably, the temperature is kept for 2 to 8 hours at the temperature of 500 to 700 ℃;
and a fifth stage: naturally cooling to room temperature.
In the present invention, it should be noted that both the second stage and the fourth stage are heat preservation stages, wherein the temperature raised in the second stage is the same as the temperature raised in the first stage, and similarly, the temperature raised in the fourth stage is the same as the temperature raised in the third stage. Specifically, for example, the first stage: heating from room temperature to 100 ℃, and then preserving heat at the temperature of 100 ℃ in the second stage; similarly, the third stage: the temperature is raised from 100 ℃ to 450 ℃, and then the fourth stage is insulated at 450 ℃.
According to the invention, the calcination is carried out in a muffle furnace, which is commercially available, and in the invention, the muffle furnace is available from Shanghai Yong Feng electric furnace Co., ltd, with the model SX2-4-10.
According to the present invention, the method further comprises drying the extruded bar precursor before the baking treatment, wherein the drying equipment is not particularly limited, for example, an oven can be used; and the drying conditions may be: drying at 110-150 deg.C for 6-8 hr.
The invention provides an anthraquinone degradation product regenerant prepared by the method.
The third aspect of the invention provides an application of the anthraquinone degradation product regenerant in the production process of hydrogen peroxide.
According to the invention, the anthraquinone is an alkyl-substituted anthraquinone, preferably the alkyl group is selected from ethyl, tert-butyl, tert-amyl or sec-amyl.
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples:
the waste clay is obtained from hydrogen peroxide production equipment of caprolactam Limited liability company Hengyi in Baling of Zhejiang.
Example 1
This example is to illustrate the anthraquinone degradation product regenerant prepared by the method of the present invention.
(1) Taking 200g of waste argil which is crushed and sieved to have the particle size of 50-100 microns, adding 3.0g of sesbania powder, 15.0g of calcium oxide powder and 2.28g of first potassium carbonate into the waste argil, and placing the mixture in a kneader to mix for 0.5h to obtain a first material; wherein the adopted waste argil is the waste argil which is withdrawn from a post-treatment argil bed and a hydrogenated argil bed in the hydrogen peroxide production process, the average particle size is 4mm, and the specific surface area is 180m 2 Per g, pore volume of 0.26cm 3 (iv) g; the waste clay contains alumina, second potassium carbonate and organic matters, and the content of the alumina is 74.9 wt%, the content of the second potassium carbonate is 1.6 wt% and the content of the organic matters is 23.5 wt% based on the total weight of the waste clay;
(2) Preparing 115.0g of a nitric acid solution with the mass fraction of 4%, and gradually adding the solution into a kneading machine for kneading to obtain a second material;
(3) Taking out the second material, extruding the second material into strips in a double-screw strip extruder, and drying the obtained strips in the shade for 24 hours at room temperature; and putting the strips obtained in the step S3 into a constant-temperature drying box for drying for 6 hours at 110 ℃, then putting the dried strips into a muffle furnace, introducing air at the flow rate of 0.9L per hour, and then starting temperature programming, wherein the temperature programming is as follows:
the first stage is as follows: heating from room temperature to 150 ℃, wherein the heating rate is 10 ℃/min;
and a second stage: keeping the temperature at 150 ℃ for 2h;
and a third stage: the temperature rise rate is 4 ℃/min, and the temperature rises to 650 ℃;
a fourth stage: keeping at 650 ℃ for 6h;
the fifth stage: and naturally cooling to room temperature.
As a result, the anthraquinone degradation product regenerant, which is marked as 10Ca3.66K-Al, was prepared 2 O 3 -R, wherein 10Ca represents the mass percentage of calcium oxide with respect to the alumina support, 3.66K represents the mass percentage of potassium carbonate with respect to the alumina support, and R represents the regenerator prepared from spent bleaching clay as a raw material. It should be noted that the potassium carbonate in this example is derived from the sum of the first potassium carbonate and the second potassium carbonate.
Example 2
This example is to illustrate the anthraquinone degradation product regenerant prepared by the method of the present invention.
An anthraquinone degradation product regenerant was prepared in the same manner as in example 1, except that: in the step (1), the mass of the added calcium oxide powder is 7.5g;
the anthraquinone degradation product regenerant is prepared as the result and is marked as 5Ca3.66K-Al 2 O 3 -R。
Example 3
This example is to illustrate the anthraquinone degradation product regenerant prepared by the method of the present invention.
An anthraquinone degradation product regenerant was prepared in the same manner as in example 1, except that: in the step (1), the mass of the added calcium oxide powder is 22.5g;
the anthraquinone degradation product regenerant is prepared by the result and is marked as 15Ca3.66K-Al 2 O 3 -R。
Example 4
This example is to illustrate the anthraquinone degradation product regenerant prepared by the method of the present invention.
An anthraquinone degradation product regenerant was prepared in the same manner as in example 1, except that: in step (1), no first potassium carbonate is added;
as a result, the anthraquinone degradation product regenerant, which is marked as 10Ca2.13K-Al, is prepared 2 O 3 -R。
Example 5
This example is to illustrate the anthraquinone degradation product regenerant prepared by the method of the present invention.
An anthraquinone degradation product regenerant was prepared in the same manner as in example 1, except that: in the step (1), the mass of the first potassium carbonate added is 3.2g;
as a result, the anthraquinone degradation product regenerant, which is marked as 10Ca4.27K-Al, is prepared 2 O 3 -R。
Example 6
This example is to illustrate the anthraquinone degradation product regenerant prepared by the method of the present invention.
An anthraquinone degradation product regenerant was prepared in the same manner as in example 1, except that: in the step (1), the mass of the added magnesium oxide is 15.0g;
as a result, an anthraquinone degradation product regenerant, which is marked as 10Mg3.66K-Al, was prepared 2 O 3 -R。
Example 7
This example is to illustrate the anthraquinone degradation product regenerant prepared by the method of the present invention.
An anthraquinone degradation product regenerant was prepared in the same manner as in example 1, except that: in the step (1), the mass of the added calcium carbonate is 26.8g;
as a result, the anthraquinone degradation product regenerant, which is marked as 10Ca3.66K-Al, was prepared 2 O 3 -R-C。
Example 8
This example is to illustrate the anthraquinone degradation product regenerant prepared by the method of the present invention.
An anthraquinone degradation product regenerant was prepared in the same manner as in example 1, except that: in the step (1), the mass of the added calcium oxide is 7.5g, and the mass of the added magnesium oxide is 7.5g;
the anthraquinone degradation product regenerant is prepared by the result and is marked as 5Ca5Mg3.66K-Al 2 O 3 -R。
Comparative example 1
Clay (Al) widely used in the industry at present was used 2 O 3 ) The small ball (diameter 3-6 mm) is used as regenerant.
Comparative example 2
A regenerant was prepared in the same manner as in example 1, except that: the spent clay was directly calcined in an air atmosphere without introducing an acid and a solid base, and the same temperature raising procedure as in example 1 was used.
The resulting regenerant, labeled 2.13K-Al, was prepared 2 O 3 -R-B。
Comparative example 3
A regenerant was prepared in the same manner as in example 1, except that: in step (1), no calcium oxide and no first potassium carbonate were added.
The resulting regenerant, labeled 2.13K-Al, was prepared 2 O 3 -R。
Comparative example 4
A regenerant was prepared in the same manner as in example 1, except that: in the step (3), in the stage heating process, the heating rate of the third stage is 4 ℃/min, and the temperature is raised to 400 ℃; the fourth stage was held at 400 ℃ for 6h.
As a result, a regenerant was prepared and was designated as 10Ca3.66K-Al 2 O 3 -R-400。
Comparative example 5
A regenerant was prepared in the same manner as in example 1, except that: in the step (3), in the stage heating process, the heating rate of the third stage is 4 ℃/min, and the temperature is raised to 800 ℃; the fourth stage was held at 800 ℃ for 6h.
As a result, a regenerant was prepared and designated as 10Ca3.66K-Al 2 O 3 -R-800。
Test example
The regeneration tests of the anthraquinone degradation product regenerants prepared in examples 1 to 8 and the regenerants prepared in comparative examples 1 to 5 on the anthraquinone degradation product in the working solution were carried out, wherein:
(1) The working solution used for evaluating the performance of the regenerant is the working solution in a hydrogen peroxide production device before a clay bed is subjected to aftertreatment, and is taken from the hydrogen peroxide production device of Hengyi caprolactam LLC of Zhejiang Baling in 2018, 8 months and 22 days. The device adopts a working solution system of ethyl anthraquinone, the content of total degradation products is about 14.4g/L, in common renewable anthraquinone degradation products, the concentration of anthrone (comprising 2-ethyl anthrone and tetrahydro-2-ethyl anthrone) is 1.6g/L, the concentration of hydroxyl anthrone (comprising 2-ethyl hydroxyl anthrone and tetrahydro-2-ethyl hydroxyl anthrone) is 3.8g/L, and the concentration of tetrahydro anthraquinone epoxide is 5.4g/L.
(2) Evaluation conditions of the regenerant: 100g of regenerant is filled into a stainless steel fixed bed, working liquid is pressurized and metered by a metering pump and then flows through a regenerant bed layer from the bottom of a reactor, and the airspeed of the working liquid is 0.90h -1 The reaction temperature was 60 ℃ and a sample was taken after 48 hours of reaction and analyzed by gas chromatography, and the results are shown in Table 1.
TABLE 1
Note 1: the effective anthraquinones in Table 1 include 2-ethylanthraquinone and tetrahydro-2-ethylanthraquinone
Note 2: r represents a regenerant prepared by taking waste clay as a raw material.
From the examples, comparative examples and table 1 it can be seen that:
(1) Compared with clay (comparative example 1), waste clay (comparative example 2) which is only roasted and a regenerant which does not contain solid alkali (comparative example 3), the regenerant can effectively improve the regeneration effect of the regenerant on anthraquinone degradation products such as anthrone, hydroxyl anthrone, tetrahydroanthraquinone epoxide and the like in working fluid, and the increase of effective anthraquinone is very remarkable.
(2) In addition, comparing example 1, example 4 and example 5 respectively, it can be seen that adding a proper amount of potassium carbonate during the preparation process is beneficial to improving the activity of the regenerant.
(3) The calcination conditions of comparative example 4 and comparative example 5 were not within the temperature range defined by the present invention, and the regeneration effect of both on the anthraquinone degradation products was significantly lower than that of example 1, indicating that the calcination temperature during the preparation process has a large influence on the performance of the regenerant.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (24)
1. A method for preparing anthraquinone degradation product regenerant by taking waste argil as raw materials is characterized by comprising the following steps:
(1) Crushing and screening the waste argil into powder with the average particle size of less than 120 mu m; mixing the crushed waste argil, the extrusion aid, the first potassium carbonate and the solid alkali to obtain a first material;
the solid alkali is selected from one or more of calcium oxide, magnesium oxide, calcium carbonate, magnesium carbonate and magnesium hydroxide; relative to 100 parts by weight of the waste argil, the amount of the extrusion aid is 0.5-10 parts by weight, the amount of the solid alkali is 2-40 parts by weight, and the amount of the first potassium carbonate is 0.5-5 parts by weight;
(2) Kneading the first material and acid to obtain a second material;
(3) Extruding the second material into strips and roasting to obtain an anthraquinone degradation product regenerant;
the roasting adopts a stage heating mode:
the first stage is as follows: heating from room temperature to 100-300 ℃, wherein the heating rate is 1-20 ℃/min;
and a second stage: preserving the heat for 1-6h at the temperature of 100-300 ℃;
and a third stage: heating from 100-300 ℃ to 450-750 ℃, wherein the heating rate is 1-15 ℃/min;
a fourth stage: preserving the heat for 1-12h at the temperature of 450-750 ℃;
and a fifth stage: naturally cooling to room temperature.
2. The method according to claim 1, wherein the waste clay is the waste clay withdrawn from a post-treatment clay bed and a hydrogenation clay bed in the hydrogen peroxide production process.
3. The method of claim 1 or 2, whereinThe average particle diameter of the waste argil is 2-6mm, and the specific surface area is 120-220m 2 Per g, pore volume of 0.2-0.3cm 3 /g。
4. The process of claim 3, wherein the spent bleaching earth comprises alumina, a second potassium carbonate, and an organic compound.
5. The method of claim 4, wherein the alumina is present in an amount of 72 to 80 wt%, the second potassium carbonate is present in an amount of 0.5 to 3 wt%, and the organic matter is present in an amount of 17 to 27.5 wt%, based on the total weight of the spent bleaching earth.
6. The process of claim 1 further comprising pulverizing and sieving the spent bleaching earth to a powder having an average particle size of 50-100 μm.
7. The method of claim 1, wherein the extrusion aid is selected from one or more of sesbania powder, cyclodextrin, and starch.
8. The method of claim 7, wherein the extrusion aid is sesbania powder.
9. The process of claim 1, wherein the solid base is selected from one or more of calcium oxide, magnesium oxide, calcium carbonate, and magnesium carbonate.
10. The method of claim 1, wherein the extrusion aid is used in an amount of 1 to 5 parts by weight, the solid base is used in an amount of 4 to 20 parts by weight, and the first potassium carbonate is used in an amount of 1 to 3 parts by weight, relative to 100 parts by weight of the spent clay.
11. The method of claim 1, wherein the acid is an aqueous solution of one or more of nitric acid, hydrochloric acid, oxalic acid, citric acid, and trichloroacetic acid.
12. The method of claim 11, wherein the acid is one or more of nitric acid, oxalic acid, and citric acid.
13. The method of claim 1 or 12, wherein the acid concentration is 1-15 wt%.
14. The method of claim 13, wherein the acid is present at a concentration of 2-10 wt.%.
15. The method of claim 1, wherein the acid is used in an amount of 40 to 90 parts by weight with respect to 100 parts by weight of the spent bleaching earth.
16. The method of claim 15 wherein the acid is used in an amount of 50 to 80 parts by weight with respect to 100 parts by weight of the spent bleaching earth.
17. The method according to claim 1, wherein, in step (2), the kneading conditions include: the temperature is 20-50 deg.C, and the time is 10-60min.
18. The method as claimed in claim 1, wherein, in the step (3), the calcination is carried out in an air atmosphere with an air flow rate of 0.1 to 3L/100 g.
19. The method as claimed in claim 18, wherein the firing is performed in an air atmosphere with an air flow rate of 0.2-1.5L/100 g.
20. The method of claim 1, wherein the first stage: heating from room temperature to 120-250 ℃, wherein the heating rate is 2-15 ℃/min;
and a second stage: preserving the heat for 2-4h at the temperature of 120-250 ℃;
and a third stage: heating from 120-250 ℃ to 500-700 ℃, wherein the heating rate is 2-10 ℃/min;
a fourth stage: preserving heat for 2-8h at the temperature of 500-700 ℃;
the fifth stage: naturally cooling to room temperature.
21. An anthraquinone degradation product regenerant prepared by the method of any one of claims 1 to 20.
22. An application of the anthraquinone degradation product regenerant as defined in claim 21 in a hydrogen peroxide production process.
23. Use according to claim 22, wherein the anthraquinone is an alkyl substituted anthraquinone.
24. Use according to claim 23, wherein the alkyl group is selected from ethyl, tert-butyl, tert-amyl or sec-amyl.
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