CN115672332A - Papermaking black liquor lignin conversion catalyst and preparation method and application thereof - Google Patents
Papermaking black liquor lignin conversion catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 130
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 59
- 229920005610 lignin Polymers 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 89
- 229910052751 metal Inorganic materials 0.000 claims abstract description 39
- 239000002184 metal Substances 0.000 claims abstract description 39
- 239000002253 acid Substances 0.000 claims abstract description 29
- 238000001035 drying Methods 0.000 claims abstract description 20
- 239000002243 precursor Substances 0.000 claims abstract description 18
- 230000009467 reduction Effects 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 9
- 238000004073 vulcanization Methods 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 238000007598 dipping method Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 31
- 230000003197 catalytic effect Effects 0.000 claims description 18
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 239000011148 porous material Substances 0.000 claims description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 7
- 244000060011 Cocos nucifera Species 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000003245 coal Substances 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea group Chemical group NC(=S)N UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002023 wood Substances 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- DZHMRSPXDUUJER-UHFFFAOYSA-N [amino(hydroxy)methylidene]azanium;dihydrogen phosphate Chemical compound NC(N)=O.OP(O)(O)=O DZHMRSPXDUUJER-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 2
- VLXBWPOEOIIREY-UHFFFAOYSA-N dimethyl diselenide Natural products C[Se][Se]C VLXBWPOEOIIREY-UHFFFAOYSA-N 0.000 claims description 2
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 239000010955 niobium Substances 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- 239000002006 petroleum coke Substances 0.000 claims description 2
- 235000011007 phosphoric acid Nutrition 0.000 claims description 2
- 238000005987 sulfurization reaction Methods 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 235000013399 edible fruits Nutrition 0.000 claims 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 1
- 239000003513 alkali Substances 0.000 abstract description 13
- 230000002378 acidificating effect Effects 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 9
- 229910052799 carbon Inorganic materials 0.000 abstract description 5
- 230000004048 modification Effects 0.000 abstract 1
- 238000012986 modification Methods 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 29
- 239000008367 deionised water Substances 0.000 description 19
- 229910021641 deionized water Inorganic materials 0.000 description 19
- 238000006136 alcoholysis reaction Methods 0.000 description 18
- 239000000243 solution Substances 0.000 description 17
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 14
- 229910052739 hydrogen Inorganic materials 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 13
- 239000001257 hydrogen Substances 0.000 description 13
- 238000005984 hydrogenation reaction Methods 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- 238000002791 soaking Methods 0.000 description 12
- 238000005303 weighing Methods 0.000 description 12
- 238000001816 cooling Methods 0.000 description 10
- 239000002808 molecular sieve Substances 0.000 description 10
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 10
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 10
- 229910000510 noble metal Inorganic materials 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- 239000004215 Carbon black (E152) Substances 0.000 description 8
- 229920001732 Lignosulfonate Polymers 0.000 description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- 229930195733 hydrocarbon Natural products 0.000 description 8
- 150000002430 hydrocarbons Chemical class 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 8
- 239000011593 sulfur Substances 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 229960001867 guaiacol Drugs 0.000 description 7
- 230000020477 pH reduction Effects 0.000 description 7
- 230000000087 stabilizing effect Effects 0.000 description 7
- 230000008569 process Effects 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 150000007522 mineralic acids Chemical class 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 238000004537 pulping Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000012670 alkaline solution Substances 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000012075 bio-oil Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 150000004687 hexahydrates Chemical class 0.000 description 2
- 238000007327 hydrogenolysis reaction Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- 125000000686 lactone group Chemical group 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000002215 pyrolysis infrared spectroscopy Methods 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000004117 Lignosulphonate Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- ZJWHOURPYIBSEK-UHFFFAOYSA-N cyclohexane triphenylphosphane Chemical compound C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1.C1CCCCC1 ZJWHOURPYIBSEK-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
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- 150000007529 inorganic bases Chemical class 0.000 description 1
- 235000019357 lignosulphonate Nutrition 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- XNHGKSMNCCTMFO-UHFFFAOYSA-D niobium(5+);oxalate Chemical compound [Nb+5].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XNHGKSMNCCTMFO-UHFFFAOYSA-D 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
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- 238000000926 separation method Methods 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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Abstract
The invention discloses a lignin conversion catalyst for papermaking black liquor, a preparation method and application thereof, and relates to the technical field of lignin conversion. The preparation method comprises the following steps: (1) Carrying out thermal reaction on an acid solution and a carrier, and washing until the pH value of a washing liquid is between 6 and 7 to obtain an acidified carrier; (2) Dipping the metal precursor on the surface of the acidified carrier to obtain a carrier loaded with metal; (3) Drying and roasting the carrier loaded with the metal to obtain roasted active carbon; (4) And (3) carrying out reduction, vulcanization or phosphorization treatment on the roasted activated carbon to obtain the lignin conversion catalyst for the papermaking black liquor. In the preparation process, alkali-resistant activated carbon is used as a carrier, so that the activated carbon has high alkali resistance and good stability under a strong alkaline condition, surface acid modification is carried out on the activated carbon, and a certain amount of acidic groups are introduced to the surface of the activated carbon, so that the activated carbon has good deoxidation activity.
Description
Technical Field
The invention relates to the technical field of lignin conversion, in particular to a lignin conversion catalyst for papermaking black liquor, and a preparation method and application thereof.
Background
The paper industry is one of the most serious industries in China. According to statistics, the discharge amount of paper product and pulping and papermaking wastewater in county and above county level of China is only inferior to the annual discharge amount of chemical raw materials and chemical product manufacturing industry. The pollution caused by the papermaking black liquor accounts for about 90 percent of the total pollution. Therefore, the treatment of the black liquor is one of the problems which are always solved at home and abroad. In the traditional alkaline pulping process, the lignin dissolved into the pulping black liquor accounts for about 30 percent of the mass of the wood raw material respectively. However, because the structure of the lignin in the papermaking black liquor is complex, the treatment difficulty is high, and the requirement on the treatment method of the lignin in the black liquor is very strict due to the strong alkalinity of the papermaking black liquor, only 5% of the lignin in the current market is consumed as low-value commodities such as low-grade fuel, concrete admixture (lignosulfonate) and the like, more than 90% of the lignin cannot be utilized, and the lignin is directly discharged as papermaking pulping waste. Therefore, the method has important practical significance for recycling and converting lignin in the papermaking black liquor into Gao Zhihua chemicals.
The existing preparation method of the lignin catalytic conversion catalyst adopts noble metal and acidic carriers such as alumina, molecular sieve and the like to carry out catalytic conversion on lignin. For example, chinese patent application 201910845937.1 discloses a black liquor lignin hydrogenolysis catalyst and a preparation method and application thereof. The catalyst comprises an HZSM-5 molecular sieve, titanium dioxide and a noble metal iridium component, wherein the load capacity of iridium on the HZSM-5 is 1wt% -30wt%, the load capacity of titanium dioxide on the HZSM-5 is 10wt% -50wt%, and the pore diameter of micropores of the catalyst is 0.55-0.60nm. The treatment method comprises the steps of firstly reacting the papermaking black liquor with inorganic acid to neutralize and remove alkali in the papermaking black liquor, then separating acid-insoluble lignosulfonate solid from reaction liquid, and then carrying out catalytic hydrogenolysis or catalytic alcoholysis on the obtained lignosulfonate to obtain lignin-based bio-oil, or continuously carrying out catalytic hydrogenation on the lignin-based bio-oil to prepare a high value-added chemical product. In this process the metal sites provide the ability to activate hydrogen to depolymerize the large lignin molecules and the acidic support provides the acidic sites to deoxygenate the resulting small lignin molecules. Although the method can effectively obtain high-value-added chemicals such as phenol and the like, the method still has many defects which can be mainly summarized as the following points: firstly, because the pH value of the papermaking black liquor is about 13, the inorganic acid and inorganic alkali resources in the papermaking black liquor are seriously wasted because the papermaking black liquor is treated by the acidification of the inorganic acid; secondly, due to the complexity of the molecular structure of the lignosulfonate, the biological oil obtained after catalytic depolymerization of the lignosulfonate has complex components and most of the components are phenolic compounds, so that the separation of a target product is difficult, and the large-scale industrial application is difficult; thirdly, due to strong basicity and high sulfur content of the papermaking black liquor, the strong basicity can seriously damage the skeleton structure of the acidic carrier to cause the inactivation of the catalyst, and the high sulfur content can quickly poison the noble metal catalyst, so that the catalyst is not suitable for a papermaking black liquor system; in addition, the noble metal catalyst is expensive and difficult to apply industrially.
Therefore, a lignin conversion catalyst for papermaking black liquor and a preparation method thereof, which have the advantages of economy, sulfur resistance, alkali resistance and high catalytic activity, are needed.
Disclosure of Invention
Based on the defects and shortcomings in the prior art, the invention provides the papermaking black liquor lignin conversion catalyst, and the preparation method and the application thereof.
The invention solves the technical problems by the following technical scheme:
in one aspect, the invention provides a preparation method of a lignin conversion catalyst for papermaking black liquor, which comprises the following steps:
(1) Carrying out thermal reaction on an acid solution and a carrier, and washing until the pH value of a washing liquid is between 6 and 7 to obtain an acidified carrier;
(2) Dipping a metal precursor on the surface of the acidified carrier prepared in the step (1) to obtain a carrier loaded with metal;
(3) And (3) drying and roasting the carrier loaded with the metal obtained in the step (2).
The acid solution in the step (1) is 1-80wt% of hydrochloric acid, phosphoric acid, sulfuric acid or nitric acid; preferably, the acid solution is 2.5wt% nitric acid or sulfuric acid.
The carrier in the step (1) is wood activated carbon, shell activated carbon, coconut shell activated carbon, coal activated carbon or petroleum coke activated carbon, and the specific surface area of the carrier is 700-2000m 2 The mass ratio of the carrier to the acid solution is 1:2-10; preferably, the carrier is coconut shell activated carbon, and the mass ratio of the carrier to the acid solution is 1:10.
the temperature of the thermal reaction in the step (1) is 40-80 ℃, and the time is 2-10h; preferably, the temperature of the thermal reaction is 50 ℃ and the time is 3h.
The metal loaded on the surface of the carrier loaded with metal in the step (2) is selected from one or two of vanadium, molybdenum, bismuth, nickel, iron, antimony, tungsten, copper, iron, niobium, chromium, magnesium, zinc and aluminum; preferably nickel.
The total atomic load of the active metal loaded on the surface of the carrier loaded with the metal in the step (2) is 5-80%.
The drying and roasting conditions in the step (3) are as follows: drying at 80-120 deg.C for 2-12 hr, and calcining at 300-550 deg.C for 2-8 hr; preferably, the drying and calcining conditions are: after drying at 120 ℃ for 4h, it was calcined at 400 ℃ for 4h.
The preparation method of the papermaking black liquor lignin conversion catalyst further comprises the step (4) of carrying out reduction, vulcanization or phosphorization treatment on the roasted carrier obtained in the step (3):
the reduction treatment conditions are as follows: the reduction temperature is 150-500 ℃, and the reduction atmosphere is H 2 Or H 2 Reducing the mixed gas of/Ar for 1-6h to obtain a reduced catalyst after treatment;
the vulcanization treatment conditions are as follows: the vulcanizing temperature is 250-500 ℃, and the vulcanizing agent is thiourea and H 2 S, DMDS and CS 2 The sulfurization time is 1-6h, and a sulfurized catalyst is obtained after treatment;
the phosphating treatment conditions are as follows: the phosphorization temperature is 250-500 ℃, the phosphorization agent is one of triphenylphosphine, phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate and urea phosphate, the phosphorization time is 1-6h, and the phosphorized catalyst is obtained after treatment.
On the other hand, the invention also provides the catalyst prepared by the preparation method, and the surface area of the catalyst is 700-1000m 2 Per g, pore volume of 0.3-0.5cm 3 Per g, the average pore diameter is 0.5-2nm, and the total acid amount on the surface is 1-8mmol/g.
On the other hand, the invention also provides the application of the catalyst prepared by the preparation method in catalytic conversion of papermaking black liquor lignin.
Compared with the prior art, the invention has the beneficial effects that:
(1) In the implementation process, alkali-resistant activated carbon is selected as a carrier, so that the catalyst has good stability under strong alkaline conditions, and the framework structure of the carrier is not damaged when the catalyst is subjected to catalytic treatment in a strong alkaline solution;
(2) In the implementation process, the activated carbon is subjected to inorganic acid heat treatment, so that hydroxyl, carboxyl and lactone groups are introduced to the surface of the activated carbon, and an acidic active site is provided for catalytic hydrodeoxygenation, so that the hydrodeoxygenation activity of the catalyst is effectively improved;
(3) The catalyst is loaded by non-noble metal, so that excellent catalytic activity can be maintained in a sulfur-containing system;
(4) The invention dries and roasts the carrier dipped with the metal precursor, and then carries out reduction, vulcanization or phosphorization, finally obtains the alkali-resistant and sulfur-resistant catalyst, and simultaneously ensures that the catalyst has good hydrogenation activity.
In the existing report, the catalyst for the lignin alcoholysis hydrodeoxygenation treatment of the papermaking black liquor takes lignosulfonate obtained after the acidification treatment of the papermaking black liquor as a raw material, adopts a noble metal catalyst and acid carriers such as alumina, molecular sieves and the like to perform catalytic conversion on lignin, and achieves the purpose of depolymerization of a lignin compound by using a metal site and the purpose of hydrodeoxygenation of the lignin compound by using an acid site. However, the acidification treatment of the black liquor causes serious waste of inorganic acid and inorganic base resources; researchers use lignosulphonate obtained by acidizing papermaking black liquor as a raw material because noble metals are easy to inactivate in the papermaking black liquor with high sulfur content, and an acidic carrier has extremely poor stability in the black liquor with strong basicity, so that satisfactory catalytic activity cannot be achieved. However, according to the preparation method of the lignin conversion catalyst for the papermaking black liquor, provided by the invention, the active carbon with high alkali resistance is used as a carrier, an acid site is introduced to the surface of the active carbon through acidification treatment, and a non-noble metal is loaded for reduction, vulcanization or phosphorization treatment, so that the catalyst with high sulfur resistance, high alkali resistance and high catalytic activity is prepared, and the stability and the catalytic activity of the catalyst in the alcoholysis hydrodeoxygenation treatment process using the papermaking black liquor as a raw material are greatly improved. Meanwhile, the catalyst prepared by the method provided by the invention has wide application range, can be applied to alkaline and non-alkaline systems such as papermaking black liquor, wood chips, lignosulfonate and the like, and greatly improves the industrial application range of the catalyst for the alcoholysis hydrodeoxygenation treatment of lignin.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
Fig. 1 is a flow chart of a preparation method of a papermaking black liquor lignin alcoholysis hydrodeoxygenation treatment catalyst in an embodiment of the invention.
FIG. 2 is an X-ray diffraction chart before and after the reaction of the sample C1 in example 1.
FIG. 3 is a BET plot before and after reaction for sample C1 in example 1.
FIG. 4 is TEM images of transmission electron micrographs before and after reaction of sample C1 in example 1.
FIG. 5 shows Py-IR patterns before and after reaction of sample C1 in example 1.
FIG. 6 is a Py-IR plot for sample E1 in comparative example 1 and C1 in example 1.
Detailed Description
The preparation method of the lignin conversion catalyst from the papermaking black liquor of the present application is described in further detail below. And do not limit the scope of the present application, which is defined by the claims. Certain disclosed specific details provide a thorough understanding of various disclosed embodiments. One skilled in the relevant art will recognize, however, that embodiments may be practiced without one or more of the specific details, with other materials, etc.
Unless the context requires otherwise, in the description and claims, the terms "comprise," comprises, "and" comprising "are to be construed in an open-ended, inclusive sense, i.e., as" including, but not limited to.
Reference in the specification to "an embodiment," "another embodiment," or "certain embodiments," etc., means that a particular described feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment. Thus, "an embodiment," "another embodiment," or "certain embodiments" do not necessarily all refer to the same embodiments. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments. Each feature disclosed in this specification may be replaced by an alternative feature serving the same, equivalent, or similar purpose. Thus, unless expressly stated otherwise, the features disclosed are merely generic examples of equivalent or similar features.
Embodiments of the present invention will be described in detail below with reference to the accompanying drawings. The following examples are only for illustrating the technical solutions of the present invention more clearly, and therefore are only examples, and the protection scope of the present invention is not limited thereby.
The reagents or drugs used in the following examples were purchased from the following vendors:
the following description is made with reference to specific embodiments.
Example 1
Weighing 2.5g of nitric acid, placing the nitric acid in a beaker, adding 97.5g of deionized water, and uniformly stirring to obtain a nitric acid solution for later use; weighing 20g of coconut shell activated carbon, placing the coconut shell activated carbon in a 500ml round-bottom flask, adding the prepared nitric acid solution, and stirring for 3 hours at 400r/min in a constant-temperature water bath at 50 ℃; washing activated carbon with a large amount of deionized water, filtering for many times until the pH value of the filtrate is between 6 and 7, and then drying in an oven at 120 ℃ for 8 hours to obtain acidified activated carbon, which is marked as S-1.
The water absorption of the carrier S-1 was measured to be 0.95ml/g, and 10g of the S-1 prepared in example 1, 7.0079g of nickel nitrate hexahydrate and 9.5g of deionized water were weighed; adding nickel nitrate hexahydrate and deionized water into a 20ml glass beaker, and placing the beaker on a magnetic stirrer to stir for 1min to obtain a metal precursor; and (3) soaking the metal precursor on the surface of S-1 by adopting an isometric impregnation method, standing at room temperature for 12h, airing, drying in a 120 ℃ oven for 2h, and roasting in a muffle furnace at 400 ℃ for 4h to obtain roasted activated carbon, which is marked as B1.
Weighing 5mlB1, placing the mixture in a fixed bed reactor, carrying out reduction treatment in a hydrogen atmosphere, introducing hydrogen (30 ml/min) until the reaction pressure is 1MPa, then starting to heat (2 ℃/min) to 400 ℃, stabilizing for 4h, cooling to room temperature, and taking out the catalyst to obtain the reduced catalyst C1.
Example 2
Weighing 5g of sulfuric acid, placing the sulfuric acid in a beaker, adding 97.5g of deionized water, and uniformly stirring to obtain a sulfuric acid solution for later use; weighing 20g of shell activated carbon, placing the 20g of shell activated carbon in a 500ml round bottom flask, adding the prepared sulfuric acid solution, stirring for 10 hours in a constant-temperature water bath at 40 ℃ at 400r/min, washing the activated carbon by using a large amount of deionized water, filtering for multiple times until the pH value of filtrate is 6-7, and drying for 8 hours in an oven at 120 ℃ to obtain acidified activated carbon, wherein the acidified activated carbon is recorded as S-2.
The water absorption of the carrier S-2 was measured to be 0.92ml/g; weighing 10g of S-2 prepared in example 1, 4.713g of nickel nitrate hexahydrate, 1.808g of ammonium paramolybdate and 9.5g of deionized water, adding the weighed materials into a 20ml glass beaker, and placing the beaker on a magnetic stirrer to stir for 1min to obtain a metal precursor; and (3) soaking the metal precursor on the surface of S-1 by adopting an isometric soaking method, standing at room temperature for 12 hours, airing, drying in an oven at 80 ℃ for 12 hours, and roasting in a muffle furnace at 450 ℃ for 8 hours to obtain roasted activated carbon, which is marked as B2.
5mlB2 was measured and placed in a fixed bed reactor at 10wt% H 2 S/H 2 Sulfurizing in atmosphere, introducing 10wt% of H 2 S/H 2 And (3) gas (30 ml/min) until the reaction pressure is 3MPa, then, heating (2 ℃/min) to 450 ℃, stabilizing for 6h, cooling to room temperature, and taking out the catalyst to obtain the sulfurized catalyst C2.
Example 3
Weighing 80g of phosphoric acid, placing the phosphoric acid in a beaker, adding 20g of deionized water, and uniformly stirring to obtain a phosphoric acid solution for later use; weighing 20g of coal-based activated carbon, placing the coal-based activated carbon in a 500ml round-bottom flask, adding the prepared phosphoric acid solution, stirring for 2 hours in a constant-temperature water bath at 80 ℃ at 400r/min, washing the activated carbon by using a large amount of deionized water, filtering for multiple times until the pH value of the filtrate is between 6 and 7, and drying for 8 hours in an oven at 120 ℃ to obtain acidified activated carbon, wherein the acidified activated carbon is recorded as S-3.
The water absorption of the carrier S-3 was measured to be 0.90ml/g; weighing 10g of S-2 prepared in example 1, 4.713g of nickel nitrate hexahydrate, 1.214g of niobium oxalate and 9.5g of deionized water, adding the weighed materials into a 20ml glass beaker, and placing the beaker on a magnetic stirrer to stir for 1min to obtain a metal precursor; and (3) soaking the metal precursor on the surface of S-3 by adopting an isometric impregnation method, standing at room temperature for 12h, airing, drying in an oven at 100 ℃ for 6h, and roasting in a muffle furnace at 350 ℃ for 8h to obtain roasted activated carbon, which is marked as B3.
Measuring 5mlB, placing the mixture in a fixed bed reactor, carrying out reduction treatment in a hydrogen atmosphere, introducing hydrogen (30 ml/min) until the reaction pressure is 2MPa, then starting to heat (2 ℃/min) to 350 ℃, stabilizing for 8h, cooling to room temperature, taking out the catalyst, and obtaining the reduced catalyst C3.
Example 4
Weighing 2g of B1 prepared in example 1, placing the B1 in a fixed bed reactor, carrying out reduction treatment in hydrogen atmosphere, introducing hydrogen (100 ml/min) until the reaction pressure is 1MPa, then starting to heat (2 ℃/min) to 450 ℃, reducing for 4h, then cooling to 200 ℃, then pumping 3wt% of triphenylphosphine cyclohexane solution, and keeping the space velocity at 2h -1 And (3) heating to 300 ℃ at a hydrogen-oil ratio of 300.
Comparative example 1
Preparing a reduced Ni/C catalyst according to the prior art: the water absorption of the coconut shell activated carbon was measured to be 0.90ml/g, and 10g of carrier AC, 7.0079g of nickel nitrate hexahydrate and 9.0g of deionized water were weighed. Adding nickel nitrate hexahydrate and deionized water into a 20ml glass beaker, and placing the beaker on a magnetic stirrer to stir for 1min to obtain a metal precursor; soaking the metal precursor on the surface of the carrier AC by an isometric soaking method, standing at room temperature for 12h, airing, drying in a 120 ℃ oven for 2h, and roasting in a muffle furnace at 400 ℃ for 4h to obtain the catalyst D1.
Placing 5ml of D1 catalyst in a fixed bed reactor, introducing hydrogen (30 ml/min) until the reaction pressure is 1MPa, then starting to heat (2 ℃/min) to 400 ℃, stabilizing for 4h, cooling to room temperature, and taking out the catalyst to obtain a reduced catalyst E1.
Comparative example 2
Preparation of reduced Ni/Al according to the prior art 2 O 3 Catalyst: measurement of support Gamma-Al 2 O 3 The water absorption of (2) was 0.65ml/g, and 10g of carrier Al was weighed 2 O 3 7.0079g nickel nitrate hexahydrate and 6.5g deionized water. Adding nickel nitrate hexahydrate and deionized water into a 20ml glass beaker, placing the beaker on a magnetic stirrer, stirring for 1min to obtain a metal precursor, and soaking the metal precursor in a carrier Al by adopting an isometric soaking method 2 O 3 And (3) placing the surface of the catalyst D2 at room temperature for 12h, airing, placing the dried surface in a 120 ℃ oven for drying for 2h, and roasting in a muffle furnace at 400 ℃ for 4h to obtain the catalyst D2.
Measuring 5ml of D2 catalyst, placing the obtained product in a fixed bed reactor, introducing hydrogen (30 ml/min) until the reaction pressure is 1MPa, then, starting to heat (2 ℃/min) to 400 ℃, stabilizing for 4h, cooling to room temperature, and taking out the catalyst to obtain the reduced catalyst E2.
Comparative example 3
Preparing a reduced Ni/USY catalyst according to the prior art: the water absorption of the carrier USY molecular sieve was measured to be 0.62ml/g, and 10g of the carrier USY molecular sieve, 7.0079g of nickel nitrate hexahydrate and 6.2g of deionized water were weighed. Adding nickel nitrate hexahydrate and deionized water into a 20ml glass beaker, placing the beaker on a magnetic stirrer, stirring for 1min to obtain a metal precursor, soaking the metal precursor on the surface of a USY molecular sieve of a carrier by an isometric soaking method, placing the USY molecular sieve at room temperature for 12h, airing, placing the USY molecular sieve in a 120 ℃ drying oven for drying for 2h, and roasting in a muffle furnace at 400 ℃ for 4h to obtain the catalyst D3.
Measuring 5ml of D3 catalyst, placing the obtained product in a fixed bed reactor, introducing hydrogen (30 ml/min) until the reaction pressure is 1MPa, then, starting to heat up (2 ℃/min) to 400 ℃, stabilizing for 4h, cooling to room temperature, and taking out the catalyst to obtain the reduced catalyst E3.
Comparative example 4
Preparing a reduced Pt/acidified active carbon catalyst according to the prior art: water absorption of S-1 prepared in example 2 was measured to be 0.95ml/g, and 10g of carrier S-1, 0.2654g of chloroplatinic acid hexahydrate and 9.5g of deionized water were weighed. Adding chloroplatinic acid hexahydrate and deionized water into a 20ml glass beaker, and placing the glass beaker on a magnetic stirrer to stir for 1min to obtain a chloroplatinic acid metal precursor solution; soaking the metal precursor solution on the surface of S-1 by an isometric soaking method, standing at room temperature for 12h, airing, drying in a 120 ℃ oven for 2h, and roasting in a muffle furnace at 400 ℃ for 4h to obtain the catalyst D1.
Measuring 5ml of D1 catalyst, placing the obtained product in a fixed bed reactor, introducing hydrogen (30 ml/min) until the reaction pressure is 1MPa, then, starting to heat up (2 ℃/min) to 400 ℃, stabilizing for 4h, cooling to room temperature, and taking out the catalyst to obtain a reduced catalyst E4.
Experimental example 1
This experimental example is to verify the catalytic action of the catalysts prepared in examples 1-4 and comparative examples 1-4 in the hydrodeoxygenation reaction of guaiacol in alkali lye, and the results are shown in Table 1.
The reaction conditions are as follows: weighing 1g of catalyst, 0.261g of NaOH, 20g of deionized water and 5g of guaiacol; reacting in a 100ml high-pressure reaction kettle, replacing air in the reaction kettle with nitrogen, and introducing hydrogen to ensure that the initial pressure is 2.5Mpa; heating to 300 ℃ at a speed of 10 ℃/min, reacting for 150min, and naturally cooling to room temperature; the catalyst was separated by centrifugation and the reaction product was analyzed by gas chromatography, the results of which are shown in Table 2 below.
TABLE 1 physicochemical Properties of the catalyst before and after the reaction
As can be seen from Table 1, the acid amount on the surface of the acid-treated activated carbon catalyst C1-C4 and the acid amount on the surface of the E1 catalyst are compared, and the acid amount on the surface of the acid-treated catalyst is obviously increased from 0.37mmol/g to 2.8-2.95mmol/g.Comparing the catalysts C1 and E1, it can be seen from FIG. 6 that, compared with the catalyst E1 without acidification treatment, the peak intensity of the characteristic corresponding to the acidic groups such as hydroxyl group on the surface of the catalyst C1 after acidification treatment is obviously improved, and the increase of the acid amount on the surface of the catalyst after acidification treatment comes from the increase of the number of the hydroxyl group, carboxyl group and lactone group, so that an acidic active site is provided for catalytic hydrodeoxygenation, thereby effectively improving the hydrodeoxygenation activity of the catalyst. Comparing the pore structure property and the acid property of C1-C4 before and after the reaction, the average pore diameter, the pore volume, the specific surface area and the surface acid amount of the catalyst after the reaction under the alkaline condition are not changed greatly, and the catalyst prepared by the invention has good stability under the alkaline condition. Comparison of E2 and E3 catalysts before and after the reaction, it was found that after the reaction under alkaline conditions, al was used 2 O 3 And the pore diameter of the catalyst taking the USY molecular sieve as the carrier is obviously enlarged, the specific surface area is obviously reduced, the framework structure of the catalyst is seriously damaged, the metal loss on the surface of the catalyst is serious, and the metal loading capacity on the surface of the catalyst is obviously reduced.
The properties of the crystal phase structure of the C1 catalyst before and after the reaction are shown in FIG. 2, the crystal phase structure of the C1 catalyst is not damaged after the catalytic reaction is carried out under the alkaline condition, and the crystal phase structure of the C1 catalyst has high stability in the alkaline solution.
The properties of the pore structure of the C1 catalyst before and after the reaction are shown in fig. 3, the pore structure of the C1 catalyst is not damaged after the catalytic reaction is performed under alkaline conditions, and the framework structure of the C1 catalyst has high stability in the alkali solution.
The microstructure of the metal crystal on the surface of the C1 catalyst before and after the reaction is shown in figure 4, the metal on the surface of the C1 catalyst still keeps a reduced metal crystal structure after the catalytic reaction is carried out in an alkaline condition, the metal crystal is uniformly dispersed without agglomeration, and the metal crystal on the surface of the C1 catalyst has high stability in alkali liquor.
The acid properties of the surface of the C1 catalyst before and after the reaction are shown in fig. 5, the types and the number of the acidic groups on the surface of the C1 catalyst after the catalytic reaction is performed under an alkaline condition are not reduced, and the C1 catalyst can maintain a certain acidity in the alkaline solution.
As can be seen from fig. 2 to 5, the physicochemical properties of the catalyst using acidic activated carbon as the carrier are not destroyed under alkaline conditions, and the catalyst has good stability.
TABLE 2 results of gas chromatography analysis of the reaction products
| Catalyst and process for producing the same | Guaiacol conversion | Yield of hydrocarbon products |
| C1 | 100％ | 27.0％ |
| C2 | 100％ | 20.5％ |
| C3 | 100％ | 45.1％ |
| C4 | 100％ | 33.2％ |
| E1 | 98.80％ | 2.5％ |
| E2 | 29.20％ | 1.1％ |
| E3 | 23.50％ | 2.3％ |
The alcoholysis hydrogenation activity of the catalyst and the hydrodeoxygenation activity of the catalyst are compared by analyzing the conversion rate of guaiacol after alcoholysis hydrogenation and the yield of hydrocarbon products, see table 2 specifically, and the results of the alcoholysis hydrogenation reaction of guaiacol on the C1 catalyst and the E1 catalyst show that although the conversion rates of the guaiacol on the two catalysts are similar, the yield of the hydrocarbon products on the acidified activated carbon catalyst C1 is obviously higher than that of the E1. By comparing the results of the alcoholysis hydrogenation reaction of guaiacol on a C1-E3 catalyst, the method is compared with that of Al 2 O 3 Compared with an E3 catalyst taking USY molecular sieve as a carrier, the E2 catalyst taking the carrier has higher hydrocarbon yield by taking the acidified active carbon as the carrier. The catalyst prepared by the method not only ensures high stability under alkaline conditions, but also ensures that certain acidic sites exist on the surface of the catalyst, and provides an effective reaction active center for the generation of hydrocarbon products.
Experimental example 2
The experimental example is a catalytic reaction of the C4 catalyst synthesized in example 4 and the E4 catalyst synthesized in comparative example 4 in a hydrodeoxygenation reaction using black liquor as a raw material, and the results are shown in table 3.
The reaction conditions are as follows: weighing 8g of catalyst, 30g of papermaking black liquor, 80g of methanol and 90g of dodecane; the reaction was carried out in a 500ml autoclave, the air in the autoclave was replaced with nitrogen, and hydrogen was introduced so that the initial pressure was 2.5MPa. Heating to 300 ℃ at a speed of 10 ℃/min, reacting for 20h, and naturally cooling to room temperature. The catalyst was separated by centrifugation, the liquid was acidified to precipitate the residual lignin solid, the liquid reaction product was analyzed by gas chromatography, the analytical results are shown in table 3 below, the residual lignin solid was characterized by elemental analysis, and the characterization results are shown in table 4 below.
TABLE 3 results of gas chromatography analysis of liquid reaction products
| Catalyst and process for preparing same | Conversion rate of black liquor lignin | Yield of hydrocarbon products |
| C4 | 66.9％ | 27.8％ |
| E4 | 2.3％ | 0.1％ |
TABLE 4 elemental analysis characterization of residual lignin solids
| Catalyst and process for preparing same | C/mol％ | H/mol％ | O/mol％ | N/mol％ | S/mol％ | H/C | O/C |
| Blank comparison | 25.9 | 41.9 | 31.2 | 0.1 | 0.7 | 1.6 | 1.2 |
| C4 | 36.6 | 47.6 | 13.7 | 0.2 | 1.9 | 1.3 | 0.4 |
| E4 | 26.0 | 42.0 | 31.2 | 0.1 | 0.7 | 1.6 | 1.2 |
In the above table 3 and table 4, the alcoholysis hydrogenation activity of the catalyst is compared by analyzing the conversion rate of the black liquor lignin after alcoholysis hydrogenation, the yield of the hydrocarbon product and the content of the O element in the residual lignin, and by comparing the alcoholysis hydrogenation reaction of the lignin on the C4 catalyst with the blank comparison result, it is found that the C4 catalyst has good catalytic activity in the alcoholysis hydrogenation reaction using the paper making black liquor as the raw material, the hydrocarbon product is effectively obtained, and the oxygen content of the lignin is reduced at the same time. By comparing the results of the alcoholysis and hydrogenation reaction of lignin on the C4 catalyst and the blank comparison, the E4 catalyst is very low in activity in the alcoholysis and hydrogenation reaction taking the papermaking black liquor as the raw material, and the Pt noble metal is rapidly poisoned by S in the papermaking black liquor. The catalyst for the alcoholysis and hydrodeoxygenation treatment of the lignin in the papermaking black liquor, which is prepared by the invention, has the advantages of economy, alkali resistance, sulfur resistance, high stability and high alcoholysis and hydrogenation activity in an alcoholysis and hydrogenation reaction taking the papermaking black liquor as a raw material.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the scope of the invention, which is defined by the claims appended hereto, and any other technical entity or method that is encompassed by the claims as broadly defined herein, or equivalent variations thereof, is contemplated as being encompassed by the claims.
Claims (10)
1. A preparation method of a lignin conversion catalyst for papermaking black liquor is characterized by comprising the following steps: the method comprises the following steps:
(1) Carrying out thermal reaction on an acid solution and a carrier, and washing until the pH value of a washing liquid is between 6 and 7 to obtain an acidified carrier;
(2) Dipping a metal precursor on the surface of the acidified carrier prepared in the step (1) to obtain a carrier loaded with metal;
(3) And (3) drying the carrier loaded with the metal obtained in the step (2) and then roasting.
2. The method of claim 1, wherein: the acid solution in the step (1) is 1-80wt% of hydrochloric acid, phosphoric acid, sulfuric acid or nitric acid, the carrier is wood activated carbon, fruit shell activated carbon, coconut shell activated carbon, coal activated carbon or petroleum coke activated carbon, and the specific surface area of the carrier is 700-2000m 2 The mass ratio of the carrier to the acid solution is1：2-10。
3. The method of claim 1, wherein: the acid solution in the step (1) is 2.5wt% of nitric acid or sulfuric acid, the carrier is coconut shell activated carbon, and the mass ratio of the carrier to the acid solution is 1:10.
4. the method of claim 1, wherein: the temperature of the thermal reaction in the step (1) is 40-80 ℃, and the time is 2-10h.
5. The method of claim 1, wherein: the metal loaded on the surface of the carrier loaded with metal in the step (2) is selected from one or two of vanadium, molybdenum, bismuth, nickel, iron, antimony, tungsten, copper, iron, niobium, chromium, magnesium, zinc and aluminum.
6. The method of claim 1, wherein: the drying and roasting conditions in the step (3) are as follows: drying at 80-120 deg.C for 2-12 hr, and calcining at 300-550 deg.C for 2-8 hr.
7. The method of claim 1, wherein: the method also comprises a step (4) of carrying out reduction, vulcanization or phosphorization treatment on the roasted carrier obtained in the step (3):
the reduction treatment conditions are as follows: the reduction temperature is 150-500 ℃, and the reduction atmosphere is H 2 Or H 2 Reducing the mixed gas of/Ar for 1-6h to obtain a reduced catalyst after treatment;
the vulcanization treatment conditions are as follows: the vulcanizing temperature is 250-500 ℃, and the vulcanizing agent is thiourea and H 2 S, DMDS and CS 2 The sulfurization time is 1-6h, and a sulfurized catalyst is obtained after treatment;
the phosphating treatment conditions are as follows: the phosphorization temperature is 250-500 ℃, the phosphorization agent is one of triphenylphosphine, phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate and urea phosphate, the phosphorization time is 1-6h, and the phosphorized catalyst is obtained after treatment.
8. A catalyst prepared by the method according to any one of claims 1 to 7.
9. The catalyst of claim 8 wherein the catalyst has a surface area of from 700 to 1000m 2 Per g, pore volume of 0.3-0.5cm 3 Per g, the average pore diameter is 0.5-2nm, and the total acid amount on the surface is 1-8mmol/g.
10. Use of a catalyst according to claim 8 or 9 for the catalytic conversion of black liquor lignin.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014108031A1 (en) * | 2013-01-08 | 2014-07-17 | 天津大学 | Use of catalyst of subgroup vi element for preparing organic chemical product from lignin |
| CN104152171A (en) * | 2014-07-24 | 2014-11-19 | 大连理工大学 | Method for preparing alkane liquid fuel by catalysis of lignin derivative aryl ether |
| CN104177223A (en) * | 2013-05-27 | 2014-12-03 | 天津大学 | Application of transition metal phosphide in catalytic conversion of lignin |
| CN104841465A (en) * | 2015-05-08 | 2015-08-19 | 中国石油大学(华东) | Load type nickel phosphide catalyst and pre-phosphating preparation method thereof |
| CN106179421A (en) * | 2016-07-19 | 2016-12-07 | 天津大学 | The preparation of sulfide catalyst and the application in lignin conversion thereof |
| SE1851510A1 (en) * | 2017-06-05 | 2018-12-06 | Suncarbon Ab | Catalytic conversion of lignin |
| CN114588910A (en) * | 2022-03-15 | 2022-06-07 | 福州大学 | Preparation method and application of Ni-Zn supported catalyst for lignin depolymerization |
-
2022
- 2022-10-12 CN CN202211247370.6A patent/CN115672332A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014108031A1 (en) * | 2013-01-08 | 2014-07-17 | 天津大学 | Use of catalyst of subgroup vi element for preparing organic chemical product from lignin |
| CN104177223A (en) * | 2013-05-27 | 2014-12-03 | 天津大学 | Application of transition metal phosphide in catalytic conversion of lignin |
| CN104152171A (en) * | 2014-07-24 | 2014-11-19 | 大连理工大学 | Method for preparing alkane liquid fuel by catalysis of lignin derivative aryl ether |
| CN104841465A (en) * | 2015-05-08 | 2015-08-19 | 中国石油大学(华东) | Load type nickel phosphide catalyst and pre-phosphating preparation method thereof |
| CN106179421A (en) * | 2016-07-19 | 2016-12-07 | 天津大学 | The preparation of sulfide catalyst and the application in lignin conversion thereof |
| SE1851510A1 (en) * | 2017-06-05 | 2018-12-06 | Suncarbon Ab | Catalytic conversion of lignin |
| CN114588910A (en) * | 2022-03-15 | 2022-06-07 | 福州大学 | Preparation method and application of Ni-Zn supported catalyst for lignin depolymerization |
Non-Patent Citations (2)
| Title |
|---|
| YANLIN XU ET.AL: ""Hydrodeoxygenation of guaiacol to bio-hydrocarbons over Ni catalyst supported on activated coconut carbon in alkaline condition "", 《BIOMASS AND BIOENERGY》, vol. 163 * |
| 杜君臣;赵永?夏文正;陈玉保;陶峰;张爱敏;: "贵金属和载体对催化剂催化脱氧裂化性能的影响", 稀有金属材料与工程, no. 09 * |
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