CN109174073A - The resource utilization method of the residual tar of kettle in a kind of production of phenylenediamine - Google Patents
The resource utilization method of the residual tar of kettle in a kind of production of phenylenediamine Download PDFInfo
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- CN109174073A CN109174073A CN201811038007.7A CN201811038007A CN109174073A CN 109174073 A CN109174073 A CN 109174073A CN 201811038007 A CN201811038007 A CN 201811038007A CN 109174073 A CN109174073 A CN 109174073A
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- China
- Prior art keywords
- kettle
- residual tar
- resource utilization
- utilization method
- phenylenediamine
- Prior art date
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- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 29
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 74
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 26
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 17
- 238000001179 sorption measurement Methods 0.000 claims abstract description 17
- 239000003463 adsorbent Substances 0.000 claims abstract description 16
- 238000003763 carbonization Methods 0.000 claims abstract description 14
- WDCYWAQPCXBPJA-UHFFFAOYSA-N 1,3-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC([N+]([O-])=O)=C1 WDCYWAQPCXBPJA-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 7
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 7
- 230000001681 protective effect Effects 0.000 claims abstract description 7
- 239000002243 precursor Substances 0.000 claims abstract description 6
- 230000006641 stabilisation Effects 0.000 claims abstract description 6
- 239000011159 matrix material Substances 0.000 claims abstract description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 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 12
- 239000000047 product Substances 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 10
- 238000005255 carburizing Methods 0.000 claims description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 235000019253 formic acid Nutrition 0.000 claims description 4
- 239000003002 pH adjusting agent Substances 0.000 claims description 4
- 230000006837 decompression Effects 0.000 claims description 3
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 3
- 239000011654 magnesium acetate Substances 0.000 claims description 3
- 235000011285 magnesium acetate Nutrition 0.000 claims description 3
- 229940069446 magnesium acetate Drugs 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N Gluconic acid Natural products OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 2
- WHMDKBIGKVEYHS-IYEMJOQQSA-L Zinc gluconate Chemical compound [Zn+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O WHMDKBIGKVEYHS-IYEMJOQQSA-L 0.000 claims description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 claims description 2
- 239000000174 gluconic acid Substances 0.000 claims description 2
- 235000012208 gluconic acid Nutrition 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 239000006210 lotion Substances 0.000 claims description 2
- 229960005336 magnesium citrate Drugs 0.000 claims description 2
- 239000004337 magnesium citrate Substances 0.000 claims description 2
- 235000002538 magnesium citrate Nutrition 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical group [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000001755 magnesium gluconate Substances 0.000 claims description 2
- 229960003035 magnesium gluconate Drugs 0.000 claims description 2
- 235000015778 magnesium gluconate Nutrition 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- IAKLPCRFBAZVRW-XRDLMGPZSA-L magnesium;(2r,3s,4r,5r)-2,3,4,5,6-pentahydroxyhexanoate;hydrate Chemical compound O.[Mg+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O IAKLPCRFBAZVRW-XRDLMGPZSA-L 0.000 claims description 2
- GMDNUWQNDQDBNQ-UHFFFAOYSA-L magnesium;diformate Chemical compound [Mg+2].[O-]C=O.[O-]C=O GMDNUWQNDQDBNQ-UHFFFAOYSA-L 0.000 claims description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 2
- 239000002594 sorbent Substances 0.000 claims description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 2
- PLSARIKBYIPYPF-UHFFFAOYSA-H trimagnesium dicitrate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O PLSARIKBYIPYPF-UHFFFAOYSA-H 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- 229960000314 zinc acetate Drugs 0.000 claims description 2
- 235000013904 zinc acetate Nutrition 0.000 claims description 2
- 239000011670 zinc gluconate Substances 0.000 claims description 2
- 235000011478 zinc gluconate Nutrition 0.000 claims description 2
- 229960000306 zinc gluconate Drugs 0.000 claims description 2
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 claims description 2
- 229940007718 zinc hydroxide Drugs 0.000 claims description 2
- 229910021511 zinc hydroxide Inorganic materials 0.000 claims description 2
- 239000000571 coke Substances 0.000 claims 1
- 230000008020 evaporation Effects 0.000 claims 1
- 238000001704 evaporation Methods 0.000 claims 1
- 239000010734 process oil Substances 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 5
- 239000001301 oxygen Substances 0.000 abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 abstract description 5
- 210000003850 cellular structure Anatomy 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 238000003672 processing method Methods 0.000 abstract description 4
- 125000003118 aryl group Chemical group 0.000 abstract description 3
- 239000005416 organic matter Substances 0.000 abstract description 3
- 239000000356 contaminant Substances 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- 150000001448 anilines Chemical class 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 8
- 238000006396 nitration reaction Methods 0.000 description 5
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 229940018564 m-phenylenediamine Drugs 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 230000004913 activation Effects 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- ZXVONLUNISGICL-UHFFFAOYSA-N 4,6-dinitro-o-cresol Chemical group CC1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1O ZXVONLUNISGICL-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- -1 aromatic amine compounds Chemical class 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 150000004986 phenylenediamines Chemical class 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- IZUKQUVSCNEFMJ-UHFFFAOYSA-N 1,2-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1[N+]([O-])=O IZUKQUVSCNEFMJ-UHFFFAOYSA-N 0.000 description 1
- FYFDQJRXFWGIBS-UHFFFAOYSA-N 1,4-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=C([N+]([O-])=O)C=C1 FYFDQJRXFWGIBS-UHFFFAOYSA-N 0.000 description 1
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 206010021703 Indifference Diseases 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 239000000981 basic dye Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000007420 reactivation Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 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
- B01J21/18—Carbon
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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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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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
- B01J35/61—Surface area
- B01J35/613—10-100 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
- B01J35/61—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
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- 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
- B01J35/617—500-1000 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
- B01J35/61—Surface area
- B01J35/618—Surface area more than 1000 m2/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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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- B01J35/635—0.5-1.0 ml/g
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- B01J35/63—Pore volume
- B01J35/638—Pore volume more than 1.0 ml/g
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- B01J35/647—2-50 nm
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/82—Purification; Separation; Stabilisation; Use of additives
- C07C209/86—Separation
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The present invention relates to phenylenediamine production technical field, a kind of resource utilization method of the residual tar of kettle in phenylenediamine production is particularly disclosed.The resource utilization method is using the residual tar of rectifying still in phenylenediamine production process as carbon source and nitrogen source, it is characterized in that: heating under microwave condition in the residual tar of kettle, auxiliary agent, template presoma addition autoclave is subjected to stabilisation pretreatment, it obtains carbon matrix precursor/template presoma mixing compound and is transferred to carbonization in tube-type atmosphere furnace, product is added acid solution and carries out template removing and wash to neutrality, is dried to obtain mesoporous carbon；Using mesoporous carbon as adsorbent, aniline in water is generated to mix dinitrobenzene hydrogenation reaction and carries out adsorbing and removing, will be recycled after the mesoporous carbon processing after adsorption saturation.Mesoporous carbon cellular structure prepared by the present invention is reasonable, and mesoporous is high, and carbon surface acidity oxygen-containing group is abundant, excellent to the adsorption effect of phenyl amines alkalescent aromatic ring organic matter；Processing method is environmentally protective, no additional contaminants discharge.
Description
(1) technical field
The present invention relates to phenylenediamine production technical field, in particular to the resource utilization of the residual tar of kettle in a kind of phenylenediamine production
Method.
(2) background technique
Phenylenediamine is a kind of important dyestuff intermediate, in all kinds of basic dyes, mordant, color developing agent, aromatic amine curing agent
The preparation field of the high performance new material of synthesis and aramid fiber 1313,1414 etc. be widely used.
Dinitrobenzene catalytic hydrogenation method is the main production process of current phenylenediamine, and technical matters can be sketched are as follows: with benzene
As initial feed, mix dinitrobenzene (dinitro is prepared by nitration reaction under nitration mixture (nitric/sulfuric acid) existence condition
Base benzene, o-dinitrobenzene, paradinitrobenzene)；Mix dinitrobenzene passes through catalytic hydrogenation reaction preparation in the presence of a catalyst
It obtains mixing phenylenediamine；Mixed diamines material passes through the isolated m-phenylene diamine (MPD) of rectifying, p-phenylenediamine and o-phenylenediamine product again.Its
In, the nitrobenzene formed on a small quantity because nitrification is not thorough, this part nitre can be contained in the mix dinitrobenzene that is obtained by nitration reaction
Base benzene directly generates aniline by subsequent catalytic hydrogenation reaction, is dissolved in the generation water of hydrogenation reaction, aniline has to pass through
Otherwise Adsorption will affect reaction and generate recycling of the water as nitration reaction wash water.Aniline adsorbent generallys use quotient
Product active carbon or macroporous absorbent resin have directly aggravated production cost since processing water causes greatly adsorbent amount more.
At the same time, the aromatic amine compounds such as m-phenylene diamine (MPD), p-phenylenediamine and o-phenylenediamine have it is easy to oxidize it is rotten,
The characteristic of polymerization coking.Phenylenediamine mixture is influenced in rectifying separation process by high temperature, and part oxidation polymerization can inevitably occur,
The burnt oil impurities for generating high molecular weight are progressively enriched in tower reactor, become dangerous waste.Such tar nitrogen content is high and sticky, at present
There is no a good processing method, most still to be handled using the methods directly burned, the shortcomings that processing method is to burn
Journey generates a large amount of toxic and harmful gas and pollutes environment, does not meet the main trend of current environmental protection and clean manufacturing；In addition, big in waste residue
The arylamine structural material of amount is not reused, and causes the great wasting of resources.Therefore, residual for kettle in phenylenediamine production
Tar carries out effectively resource utilization and is of great significance
(3) summary of the invention
In order to compensate for the shortcomings of the prior art, the present invention provides a kind of environmentally protective, efficient matchings prior art phenylenediamines
The resource utilization method of the residual tar of kettle in production.
The present invention is achieved through the following technical solutions:
The resource utilization method of the residual tar of kettle in a kind of production of phenylenediamine, with the residual tar of rectifying still in phenylenediamine production process
As carbon source and nitrogen source, wherein the nitrogen content of the residual tar of kettle is 10-25%, is included the following steps:
(1) the residual tar of kettle, auxiliary agent, template presoma are added in the autoclave for being equipped with microwave device, are passed through compressed air,
Heating stirring carries out stabilisation pretreatment under microwave condition, obtains the uniformly mixed compound of carbon matrix precursor/template presoma；
(2) above-mentioned compound is transferred in tube-type atmosphere furnace, is carbonized in the case where protecting gas existence condition according to temperature programming,
The obtained product that is carbonized is added acid solution and carries out template removing and be washed with deionized to neutrality, is dried to obtain mesoporous carbon；
(3) using mesoporous carbon as adsorbent, aniline in water is generated to mix dinitrobenzene hydrogenation reaction and carries out adsorbing and removing, after adsorbing
Water phase meet the requirement that uses as nitration reaction wash water；
(4) mesoporous carbon after adsorption saturation is subjected to decompression baking, the aniline evaporated is condensed and is collected, after processing mesoporous carbon
It is used as sorbent circulation.
The present invention is led under acid catalysed conditions using the residual tar of rectifying still in phenylenediamine production process as carbon source and nitrogen source
Cross high pressure air oxidation polymerization realize stabilize pretreatment, then with nano-metal-oxide template presoma (organic acid metal
Salt compounds) it is thoroughly mixed to form just casting material, during tar polymer high temperature cabonization, template presoma is thermally decomposed
Form the oxide particle of nanoscale, it is continuous it is embedding be loaded in inside carbonized product, and after after the dissolution of corresponding acid solution, in carbon
The inside for changing product forms abundant and continuous mesoporous scale cellular structure；Nitrogen is one in carbonisation in tar polymer
Part is retained, and doping enters carbon residue structure, generates modulation to the surface chemical property of carbon, another part then decomposes generation nitrogen
The oxidizing gas such as oxide, so that carbon residue body structure surface aoxidizes to form acid oxygen-containing group；With the above-mentioned surface being prepared
The adsorbent for generating aniline in water as hydrogenation reaction containing the mesoporous carbon materials for containing abundant acid oxygen-containing group, can significantly improve
The adsorbance of aniline.
More excellent technical solution of the invention are as follows:
In step (1), auxiliary agent is one of formic acid, acetic acid, citric acid, p-methyl benzenesulfonic acid, the quality of kettle residual tar and auxiliary agent
Than for 1:0.001-0.01.
Template presoma is magnesium formate, in magnesium acetate, magnesium citrate, magnesium gluconate, zinc acetate, zinc gluconate
The mass ratio of one kind, the residual tar of kettle and template presoma is 1:0.1-10.
Microwave power is 500-3000W, speed of agitator 500-1500rpm in autoclave.
In step (2), protective gas is one of high pure nitrogen, high-purity helium, high-purity argon gas；The heating of carbonisation
Rate is 0.5-10 DEG C/min, and highest carburizing temperature is 700-1000 DEG C, and highest carburizing temperature is held time as 0.5-5hr.
Acid solution is one of aqueous formic acid, aqueous acetic acid, aqueous citric acid solution or gluconic acid solution.
Filtrate and water lotion mixed collection after template removal, are added the excess acid in pH adjusting agent and in solution, steam
Hair is concentrated into required concentration to get to template precursor solution, is recycled；Wherein, the pH adjusting agent is magnesium hydroxide
Or zinc hydroxide.
The tail gas of carbonisation is absorbed using the mesoporous carbon prepared as adsorbent.
Mesoporous carbon cellular structure prepared by the present invention is reasonable, and mesoporous is high, and carbon surface acidity oxygen-containing group is abundant, to aniline
The adsorption effect of class alkalescent aromatic ring organic matter is excellent；Compared with prior art, processing method is environmentally protective, no additional contaminants
It discharges, required raw material can be recycled in entire technical solution implementation process, does not result in waste of resources, both realizes phenylenediamine
The high-efficiency resource recycling of the residual tar of kettle in production, and generate water for hydrogenation reaction and provide efficient aniline adsorbent.
(4) Detailed description of the invention
The present invention will be further described below with reference to the drawings.
Fig. 1 is the SEM photograph figure of N-MC-1 in embodiment 1；
Fig. 2 is the SEM photograph figure of N-C-1 in embodiment 2.
(5) specific embodiment
Below with reference to embodiment, the invention will be further described.
Embodiment 1:
The resource utilization method of the residual tar of kettle in a kind of production of phenylenediamine, with the residual tar of rectifying still in phenylenediamine production process
As carbon source and nitrogen source, wherein the nitrogen content of the residual tar of kettle is 15%, it is characterized in that, include the following steps:
(1) the residual tar of 300g kettle, 0.3g acetic acid, 150g magnesium acetate are added and are equipped with microwave device, the reaction that capacity is 1000mL
In kettle, it is passed through compressed air, heating stirring carries out stabilisation pretreatment, speed of agitator under the conditions of the microwave irradiation of 500W
1000rpm obtains the uniformly mixed compound of carbon matrix precursor/template presoma；
(2) above-mentioned compound is transferred in tube-type atmosphere furnace, heat up according to the procedure below under high pure nitrogen existence condition into
Row carbonization: heating rate is 1 DEG C/min, 800 DEG C of highest carburizing temperature, highest carburizing temperature are held time 5hr.It is obtained through carbonization
Product acetum be added template removing and be washed with deionized to neutrality, be dried to obtain about 140g mesoporous carbon, remember
For N-MC-1；
(3) it takes 10g mesoporous carbon obtained above as adsorbent, hydrogen is added to 1000g mix dinitrobenzene using Static Adsorption mode
Reaction generates the aniline in water and carries out adsorbing and removing, and concentration of aniline is 2000ppm in original water phase, after single adsorptions in water phase
Concentration of aniline is down to about 18ppm, and aniline removal rate is about 99.1%；Mesoporous carbon is recycled after simple filtration, according to identical
Ratio is continuously adsorbed 5 times, and water phase concentration of aniline is 40ppm after adsorbing for the last time；
(4) mesoporous carbon after adsorption saturation is subjected to decompression baking, by the aniline evaporated condense collect, after regeneration treatment in
Hole carbon is denoted as N-MC-1a, is recycled: according to identical adsorbent in step (3)/watr-proportion processing, after single adsorptions
Concentration of aniline is down to about 20ppm, adsorption effect and the basic indifference of fresh mesoporous carbon by 2000ppm in water phase.
Embodiment 2:
Using the residual tar of phenylenediamine rectifying still in the same manner as in Example 1 as carbon source and nitrogen source, and using in the same manner as in Example 1
Preprocess method stabilisation pretreatment is carried out to the residual tar of kettle, template presoma is not added in unique difference only；It will be through
The residual tar of the pretreated kettle of overstabilization is directly transferred in tube-type atmosphere furnace, according to program liter under high pure nitrogen existence condition
Temperature carbonization, protective atmosphere flow, heating rate, highest carburizing temperature and highest carburizing temperature are held time and in embodiment 1
Completely the same, the product for the completion that is carbonized carries out stripper plate processing, carbide note obtained using method in the same manner as in Example 1
For N-C-1.
Using N-C-1 as adsorbent, mix dinitrobenzene is added using with step (3) identical method in embodiment 1
Hydrogen reaction generates the aniline in water and carries out adsorbing and removing, and concentration of aniline is down to about by 2000ppm in water phase after single adsorptions
1530ppm, aniline removal rate are only 23.5%.
Embodiment 3:
Using preparation method identical with C-1 in embodiment 2, it is passed through vapor high-temperature activation, steam again after carbonisation
Flow is 20mL/min, and activation temperature is 850 DEG C, activation time 5hr.Finished catalyst obtained is denoted as N-AC-1.
Using N-AC-1 as adsorbent, mix dinitrobenzene is added using with step (3) identical method in embodiment 1
Hydrogen reaction generates the aniline in water and carries out adsorbing and removing, and concentration of aniline is down to about by 2000ppm in water phase after single adsorptions
410ppm, aniline removal rate are 79.5%.
Embodiment 4:
Only using phenolic resin as carbon source replace phenylenediamine production process in the residual tar of rectifying still, using with it is complete in embodiment 1
Exactly the same stabilisation pre-processes, prepared by compound, the processing such as high temperature cabonization and sour solution-off removing template carry out under protective atmosphere
The preparation of mesoporous carbon, finished product mesoporous carbon obtained are denoted as MC-1.
Using MC-1 as adsorbent, hydrogen is added to mix dinitrobenzene using with step (3) identical method in embodiment 1
Reaction generates the aniline in water and carries out adsorbing and removing, and concentration of aniline is down to about by 2000ppm in water phase after single adsorptions
190ppm, aniline removal rate are 90.5%；Mesoporous carbon is recycled after simple filtration, continuously adsorbs 5 according to same ratio
Secondary, water phase concentration of aniline is 530ppm after adsorbing for the last time, apparent raising occurs.
Embodiment 5: absorption comparative experiments
Using merchandise active carbon 3SW as adsorbent, using with step (3) identical method in embodiment 1 to mixed dinitro
Base benzene hydrogenation generates the aniline in water and carries out adsorbing and removing, and concentration of aniline is dropped by 2000ppm in water phase after single adsorptions
To about 132ppm, aniline removal rate is 93.4%；Active carbon is reused after simple filtration, aniline in water phase after the 2nd absorption
Concentration is down to about 372ppm by 2000ppm, that is, more apparent raising occurs.
Catalyst characterization: N-C-1, N-AC-1, the MC-1 prepared in N-MC-1, the embodiment 2-4 prepared in embodiment 1 with
And commercialization 3SW uses SEM, N2Low-temperature physics absorption, Boehm titration and gravimetric titrimetry method carry out phenetic analysis.
The mesoporous carbon N-MC-1 and MC-1 prepared with embedded template method is used it can be seen from the analysis result of table 1, compares table
Area is higher, and mesoporous plot ratio can achieve 93% or more, and average pore size concentrates on 7nm or so, theoretically can be this kind of for aniline
The biggish aromatic ring organic matter of molecule provides good diffusion admittance and attachment space；And the carbon material N- prepared with direct carborization
For C-1 compared with N-MC-1 and MC-1, specific surface area and mesoporous plot ratio are minimum, and average pore size also very little (1.5nm or so) infers
The porosity that the residual tar of kettle spontaneously forms during direct carbonization is extremely low；It may determine that by N-AC-1, although reactivation process
It can increase a part of specific surface area and mesoporous, but promote limited extent, average pore size or relatively small is overall with micropore
Based on.And although commercial activated charcoal 3SW specific surface area is larger, it is overall be also distributed with micropore based on.
By the analysis result of table 2 it can be found that in the residual tar carbonisation of kettle, nitrogenous structure division is heated to be decomposed into dioxy
Changing the oxidizing atmospheres such as nitrogen can promote to form oxygen-containing group (N-MC-1, N-C-1, N- more abundant on carbonized product surface
AC-1), overall in acidity so that carbon surface point of zero electric charge is lower；In contrast, using phenolic resin as carbon source system in embodiment 4
Standby obtained MC-1, since itself cannot form the oxidizing atmospheres such as nitrogen dioxide, finally obtain without N structure, carbonisation is contained
Carbonized product acidic oxygenous group on surface amount it is few, carbon surface point of zero electric charge is higher, it is overall present it is neutral to alkalescent.Due to
The aniline being adsorbed is alkalescent, and adsorbent surface acidic environment is conducive to the absorption of aniline, and therefore, the adsorption effect of aniline is same
When influenced by carbon material cellular structure and surface chemical property.The characterization result of table 1-2 and the adsorption experiment knot of embodiment 1-5
Fruit corresponds to each other.
And by the analysis result of the SEM of N-MC-1 and N-C-1 it can also be seen that the perforating action of template makes N-MC-1
Surface topography and N-C-1 generate notable difference, the surface N-MC-1 duct structure-rich is obvious, and N-C-1 smooth surface, hole
Rate is low.
Claims (9)
1. the resource utilization method of the residual tar of kettle in a kind of phenylenediamine production, with the residual coke of rectifying still in phenylenediamine production process
Oil is used as carbon source and nitrogen source, wherein and the nitrogen content of the residual tar of kettle is 10-25%, it is characterized in that, include the following steps: (1) by kettle
Residual tar, auxiliary agent, template presoma are added in the autoclave for being equipped with microwave device, are passed through compressed air, under microwave condition
Heating stirring carries out stabilisation pretreatment, obtains the uniformly mixed compound of carbon matrix precursor/template presoma；It (2) will be above-mentioned
Compound is transferred in tube-type atmosphere furnace, is carbonized in the case where protecting gas existence condition according to temperature programming, is obtained through carbonization
Product is added acid solution and carries out template removing and be washed with deionized to neutrality, is dried to obtain mesoporous carbon；(3) it is with mesoporous carbon
Adsorbent generates aniline in water to mix dinitrobenzene hydrogenation reaction and carries out adsorbing and removing, and the water phase after adsorbing, which meets, is used as nitre
Change the requirement that reaction wash water uses；(4) mesoporous carbon after adsorption saturation is subjected to decompression baking, the aniline evaporated is condensed and is received
Collection, mesoporous carbon is used as sorbent circulation after processing.
2. the resource utilization method of the residual tar of kettle in phenylenediamine production according to claim 1, it is characterised in that: step
(1) in, auxiliary agent is one of formic acid, acetic acid, citric acid, p-methyl benzenesulfonic acid, and the mass ratio of the residual tar of kettle and auxiliary agent is 1:
0.001-0.01。
3. the resource utilization method of the residual tar of kettle in phenylenediamine production according to claim 1, it is characterised in that: step
(1) in, template presoma is magnesium formate, magnesium acetate, magnesium citrate, magnesium gluconate, zinc acetate, one in zinc gluconate
Kind, the mass ratio of the residual tar of kettle and template presoma is 1:0.1-10.
4. the resource utilization method of the residual tar of kettle in phenylenediamine production according to claim 1, it is characterised in that: step
(1) in, microwave power is 500-3000W, speed of agitator 500-1500rpm in autoclave.
5. the resource utilization method of the residual tar of kettle in phenylenediamine production according to claim 1, it is characterised in that: step
(2) in, protective gas is one of high pure nitrogen, high-purity helium, high-purity argon gas；The heating rate of carbonisation is 0.5-10
DEG C/min, highest carburizing temperature is 700-1000 DEG C, and highest carburizing temperature is held time as 0.5-5hr.
6. the resource utilization method of the residual tar of kettle in phenylenediamine production according to claim 1, it is characterised in that: step
(2) in, acid solution is one of aqueous formic acid, aqueous acetic acid, aqueous citric acid solution or gluconic acid solution.
7. the resource utilization method of the residual tar of kettle in phenylenediamine production according to claim 1, it is characterised in that: step
(2) in, the excess acid in pH adjusting agent and in solution, evaporation is added in filtrate and water lotion mixed collection after template removal
Required concentration is concentrated into get to template precursor solution, is recycled.
8. the resource utilization method of the residual tar of kettle in phenylenediamine production according to claim 1, it is characterised in that: step
(2) in, the tail gas of carbonisation is absorbed using the mesoporous carbon prepared as adsorbent.
9. the resource utilization method of the residual tar of kettle in phenylenediamine production according to claim 7, it is characterised in that: described
PH adjusting agent is magnesium hydroxide or zinc hydroxide.
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