CN107497476A - A kind of modified zeolite molecular sieve solid acid catalyst and preparation method thereof, application - Google Patents
A kind of modified zeolite molecular sieve solid acid catalyst and preparation method thereof, application Download PDFInfo
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- CN107497476A CN107497476A CN201710736703.4A CN201710736703A CN107497476A CN 107497476 A CN107497476 A CN 107497476A CN 201710736703 A CN201710736703 A CN 201710736703A CN 107497476 A CN107497476 A CN 107497476A
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- molecular sieve
- zeolite molecular
- modified zeolite
- acid
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 134
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 134
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical class O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 239000003054 catalyst Substances 0.000 title claims abstract description 84
- 239000011973 solid acid Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims description 22
- -1 lutetium ion Chemical class 0.000 claims abstract description 66
- 238000000034 method Methods 0.000 claims abstract description 36
- 229910052706 scandium Inorganic materials 0.000 claims abstract description 18
- 229910052769 Ytterbium Inorganic materials 0.000 claims abstract description 10
- 229910052689 Holmium Inorganic materials 0.000 claims abstract description 9
- 229910001430 chromium ion Inorganic materials 0.000 claims abstract description 9
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 9
- 239000010955 niobium Substances 0.000 claims abstract description 9
- WCWKKSOQLQEJTE-UHFFFAOYSA-N praseodymium(3+) Chemical compound [Pr+3] WCWKKSOQLQEJTE-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052693 Europium Inorganic materials 0.000 claims abstract description 8
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910001449 indium ion Inorganic materials 0.000 claims abstract description 8
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052765 Lutetium Inorganic materials 0.000 claims abstract description 7
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 7
- 229910052775 Thulium Inorganic materials 0.000 claims abstract description 7
- RJOJUSXNYCILHH-UHFFFAOYSA-N gadolinium(3+) Chemical compound [Gd+3] RJOJUSXNYCILHH-UHFFFAOYSA-N 0.000 claims abstract description 7
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 48
- 239000002253 acid Substances 0.000 claims description 27
- 239000004310 lactic acid Substances 0.000 claims description 24
- 235000014655 lactic acid Nutrition 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 23
- 238000005342 ion exchange Methods 0.000 claims description 22
- 230000004044 response Effects 0.000 claims description 22
- 229910021536 Zeolite Inorganic materials 0.000 claims description 20
- 239000010457 zeolite Substances 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 16
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 238000012805 post-processing Methods 0.000 claims description 14
- 239000011148 porous material Substances 0.000 claims description 13
- 239000002028 Biomass Substances 0.000 claims description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 11
- 239000007791 liquid phase Substances 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 11
- 229910017604 nitric acid Inorganic materials 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 6
- 238000001802 infusion Methods 0.000 claims description 5
- 239000002502 liposome Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000002105 nanoparticle Substances 0.000 claims description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 4
- 239000004327 boric acid Substances 0.000 claims description 4
- 244000025254 Cannabis sativa Species 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 230000001351 cycling effect Effects 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 description 23
- 240000003183 Manihot esculenta Species 0.000 description 16
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 16
- 239000000243 solution Substances 0.000 description 14
- 239000003643 water by type Substances 0.000 description 11
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 9
- 238000003756 stirring Methods 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- DVMZCYSFPFUKKE-UHFFFAOYSA-K scandium chloride Chemical class Cl[Sc](Cl)Cl DVMZCYSFPFUKKE-UHFFFAOYSA-K 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- 239000010703 silicon Substances 0.000 description 7
- 238000003912 environmental pollution Methods 0.000 description 4
- 229910052738 indium Inorganic materials 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 206010013786 Dry skin Diseases 0.000 description 3
- 244000061456 Solanum tuberosum Species 0.000 description 3
- 235000002595 Solanum tuberosum Nutrition 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000005660 chlorination reaction Methods 0.000 description 3
- 238000000855 fermentation Methods 0.000 description 3
- 230000004151 fermentation Effects 0.000 description 3
- 235000006408 oxalic acid Nutrition 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 235000017060 Arachis glabrata Nutrition 0.000 description 2
- 244000105624 Arachis hypogaea Species 0.000 description 2
- 235000010777 Arachis hypogaea Nutrition 0.000 description 2
- 235000018262 Arachis monticola Nutrition 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000002242 deionisation method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 2
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical class O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000012982 microporous membrane Substances 0.000 description 2
- 238000013386 optimize process Methods 0.000 description 2
- 235000020232 peanut Nutrition 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 241000370738 Chlorion Species 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229920000704 biodegradable plastic Polymers 0.000 description 1
- 239000002551 biofuel Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229930002839 ionone Natural products 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical class Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 description 1
- LHBNLZDGIPPZLL-UHFFFAOYSA-K praseodymium(iii) chloride Chemical class Cl[Pr](Cl)Cl LHBNLZDGIPPZLL-UHFFFAOYSA-K 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- 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
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/37—Acid treatment
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
Abstract
The invention provides a kind of modified zeolite molecular sieve solid acid catalyst, including modified zeolite molecular sieve and the active component that is supported on the modified zeolite molecular sieve；The active component includes the one or more in chromium ion, praseodymium ion, lutetium ion, niobium ion, holmium ion, thulium ion, gadolinium ion, samarium ion, ruthenium ion, europium ion, ytterbium ion, neodymium ion, dysprosium ion, indium ion and scandium ion.The invention provides a kind of modified zeolite molecular sieve solid acid catalyst, using specific active component, have catalytic activity high, selective good, catalyst is easily isolated and recycled, it can be recycled and the advantage such as good cycling stability, and the method for preparing catalyst is simple, environmentally friendly pollution-free.
Description
Technical field
The invention belongs to molecular sieve catalyst technical field, be related to a kind of modified zeolite molecular sieve solid acid catalyst and its
Preparation method, application, more particularly to a kind of modified zeolite molecular sieve solid acid catalyst and preparation method thereof, in biomass material
Application in catalytic cracking lactic acid.
Background technology
With fossil resource peter out and caused problem of environmental pollution getting worse, find using can be again
Raw, degradable clean energy resource has turned into one of major issue that the mankind are faced.Therefore, biomass resource is as in nature
The renewable resource of rich reserves, it will solve crisis of resource to be efficiently converted into the bio-fuel of high added value and chemicals
With the effective means of environmental pollution, have great importance.
In many biomass resources, leaf, stalk, peanut shell, potato class etc., all with sizable yield, have
Very high Utilization prospects, particularly tapioca are the very abundant biomass resources of South China of China content, with state
Family's environmental requirement increasingly improve and increasingly increase of the relevant industries to tapioca demand both at home and abroad, tapioca by
One of " six big pillar industries " that South China will give priority in particularly Guangxi future is classified as, therefore, tapioca will turn into ring
Border is protected and the important selection of the Sustainable Development Strategy.
Lactic acid, also known as be a kind of important chemical platform compound of Lactic acid, it is widely used in food, medicine, skin
In the industries such as leather, cosmetics and biodegradable plastic.
From the point of view of current research report, production of lactic acid mainly uses biological fermentation process and chemical synthesis, but fermentation method institute
The price of the biology enzyme used is higher, and technological process is complicated, fermentation time length, and lactic acid yield is relatively low, such as patent CN
There is related record in 101168754A, CN 1171844C to CN 102533878A, be unfavorable for industrialized production.
Chemical synthesis is urged mainly using biomass as raw material using liquid mineral acid, homogeneous lewis acid, inorganic base etc.
Agent, such as patent CN 102603512, and document J Chem Technol Biotechnol, 2008,83:383-388 and
AIChE,2010,56(10):There are record and the report of correlation in 2727-2733., but these catalysis are used in actual production
Not the problems such as agent does not only exist corrosive equipment, catalyst is difficult to separate, environmental pollution is more serious, and lactic acid yield is relatively low
The shortcomings of, it is unfavorable for industrialized production and the application of lactic acid.
Therefore, how to find a kind of method using green catalysis conversion tapioca is converted into high added value
Lactic acid chemicals, overcome drawbacks described above, it has also become many forward-looking research staff widely focus of attention in field
One of, there is important society and economic implications.
The content of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of modified zeolite molecular sieve solid acid catalyst
And preparation method thereof, application, the particularly application in biomass material catalytic cracking lactic acid, modified boiling provided by the invention
Stone molecular sieve solid acid catalyst preparation method is simple, catalytic activity is high, be easily isolated and recycled, good cycling stability, to environment
It is friendly pollution-free, it is easy to accomplish large-scale production.
The invention provides a kind of modified zeolite molecular sieve solid acid catalyst, including modified zeolite molecular sieve and it is supported on
Active component on the modified zeolite molecular sieve；
The active component include chromium ion, praseodymium ion, lutetium ion, niobium ion, holmium ion, thulium ion, gadolinium ion, samarium from
One or more in son, ruthenium ion, europium ion, ytterbium ion, neodymium ion, dysprosium ion, indium ion and scandium ion.
Preferably, the load capacity of the active component is 10wt%~30wt%；
The modified zeolite molecular sieve is sour modified zeolite molecular sieve；
The zeolite molecular sieve includes the one or more in type ZSM 5 molecular sieve, beta molecular sieve and HY type molecular sieves.
Preferably, the specific surface area of the modified zeolite molecular sieve is 328.6~448.9m2·g-1；
The pore volume of the modified zeolite molecular sieve is 0.19~0.35cm3·g-1；
The aperture of the modified zeolite molecular sieve is 2.31~3.51nm；
The sial atomic ratio of the modified zeolite molecular sieve is 8.93~197.6.
The invention provides a kind of preparation method of modified zeolite molecular sieve solid acid catalyst, comprise the following steps：
1) after zeolite molecular sieve is mixed with acid, heating response, modified zeolite molecular sieve is obtained；
2) after being loaded using the salt containing active component on the modified zeolite molecular sieve that above-mentioned steps obtain, obtain
Modified zeolite molecular sieve solid acid catalyst.
Preferably, the acid includes the one or more in nitric acid, hydrochloric acid, sulfuric acid, boric acid, oxalic acid, citric acid；
The temperature of the heating response is 60~100 DEG C；
The time of the heating response is 5~15 hours.
Preferably, the method for the load includes liquid-phase ion exchange, infusion process or solid liposome nanoparticle method；
When the method for the load is liquid-phase ion exchange, the preparation method is specially：
A) after zeolite molecular sieve is mixed with acid solution, heating response, modified zeolite molecular sieve is obtained；
B) modified zeolite molecular sieve, the soluble-salt containing active component and the water obtained above-mentioned steps mixes again
Afterwards, obtain exchanging modified molecular screen presoma；
C) the exchange modified molecular screen presoma for obtaining above-mentioned steps obtains modified zeolite molecular sieve and consolidated after roasting
Body acid catalyst.
Preferably, the concentration of the acid solution is 10wt%~30wt%；
The mass ratio of the zeolite molecular sieve and acid solution is 1：(20~100).
Preferably, post-processing step is also included after the heating response；
The time mixed again is 6~24 hours；
The temperature mixed again is 80~120 DEG C；
Also include post-processing step again after the mixing again；
The post-processing step includes the one or more in standing, separate, being filtered, washed and dried.
Preferably, the temperature of the roasting is 400~700 DEG C；
The time of the roasting is 10~12 hours.
Present invention also offers the modified zeolite molecular sieve solid acid catalyst described in above-mentioned technical proposal any one or
Application of the solid acid catalyst in catalyzed conversion biomass material lactic acid prepared by above-mentioned technical proposal any one.
The invention provides a kind of modified zeolite molecular sieve solid acid catalyst, including modified zeolite molecular sieve and it is supported on
Active component on the modified zeolite molecular sieve；The active component includes chromium ion, praseodymium ion, lutetium ion, niobium ion, holmium
In ion, thulium ion, gadolinium ion, samarium ion, ruthenium ion, europium ion, ytterbium ion, neodymium ion, dysprosium ion, indium ion and scandium ion
One or more.Compared with prior art, the present invention be directed to corrosive equipment existing for existing lactic acid used catalyst processed,
A kind of the shortcomings of catalyst is difficult to separate, environmental pollution is more serious, and lactic acid yield is relatively low, there is provided modified zeolite point
Son sieve solid acid catalyst, using specific active component, have catalytic activity high, selective good, catalyst is easily isolated back
Receive, can be recycled and the advantage such as good cycling stability, and the method for preparing catalyst is simple, environmentally friendly pollution-free.
Test result indicates that modified zeolite molecular sieve solid acid catalyst provided by the invention, for catalyzed conversion cassava
The catalytic activity of starch lactic acid is high, selective good, and catalyst is easily isolated and recycled, and good cycling stability, and can be complete
Full catalyzed conversion tapioca, lactic acid yield reach more than 65%.
Embodiment
For a further understanding of the present invention, the preferred embodiment of the invention is described with reference to embodiment, still
It should be appreciated that these descriptions are intended merely to further illustrate the features and advantages of the present invention, rather than to invention claim
Limitation.
All raw materials of the present invention, its source is not particularly limited, commercially buying or according to people in the art
Known to member prepared by conventional method.
All raw materials of the present invention, its purity is not particularly limited, and present invention preferably employs analyze pure or solid acid catalysis
The conventional purity in agent field.
The invention provides a kind of modified zeolite molecular sieve solid acid catalyst, including modified zeolite molecular sieve and it is supported on
Active component on the modified zeolite molecular sieve；
The active component include chromium ion, praseodymium ion, lutetium ion, niobium ion, holmium ion, thulium ion, gadolinium ion, samarium from
One or more in son, ruthenium ion, europium ion, ytterbium ion, neodymium ion, dysprosium ion, indium ion and scandium ion.
The modification mode of the modified zeolite molecular sieve is not particularly limited the present invention, with known to those skilled in the art
Modification mode, those skilled in the art can be selected and adjusted according to applicable cases, product requirement and quality requirement
Whole, modified zeolite molecular sieve of the present invention is preferably sour modified zeolite molecular sieve.
The particular type of the zeolite molecular sieve is not particularly limited the present invention, with well known to those skilled in the art normal
Advise zeolite molecular sieve, those skilled in the art can be selected according to applicable cases, product requirement and quality requirement and
Adjustment, zeolite molecular sieve of the present invention preferably include one kind in type ZSM 5 molecular sieve, beta molecular sieve and HY type molecular sieves
Or a variety of, more preferably type ZSM 5 molecular sieve, beta molecular sieve or HY type molecular sieves, most preferably include type ZSM 5 molecular sieve.
Active component of the present invention include chromium ion, praseodymium ion, lutetium ion, niobium ion, holmium ion, thulium ion, gadolinium from
One or more in son, samarium ion, ruthenium ion, europium ion, ytterbium ion, neodymium ion, dysprosium ion, indium ion and scandium ion, more
Preferably chromium ion, praseodymium ion, lutetium ion, niobium ion, holmium ion, thulium ion, gadolinium ion, samarium ion, ruthenium ion, europium ion,
Ytterbium ion, neodymium ion, dysprosium ion, indium ion or scandium ion, more preferably chromium ion, praseodymium ion, niobium ion, gadolinium ion, yttrium from
Son, europium ion, ytterbium ion, neodymium ion, dysprosium ion or scandium ion, most preferably scandium ion.
The load capacity of the activearm is not particularly limited the present invention, with conventional load well known to those skilled in the art
Amount, those skilled in the art can be selected and adjusted according to applicable cases, product requirement and quality requirement, the present invention
The load capacity of the active component is preferably 10wt%~30wt%, more preferably 12wt%~28wt%, more preferably
15wt%~25wt%, more preferably 17wt%~23wt%.
The design parameter of the modified zeolite molecular sieve solid acid catalyst is not particularly limited the present invention, with this area
The parameter of conventional such product known to technical staff, those skilled in the art can be according to applicable cases, product requirement
Selected and adjusted with quality requirement, present invention preferably employs specific sour modified zeolite molecular sieve, the modified zeolite
Molecular sieve solid acid catalyst has better performance parameter, and the specific surface area of the modified zeolite molecular sieve is preferably 328.6
~448.9m2·g-1, more preferably 325~445m2·g-1, more preferably 320~440m2·g-1, more preferably 325~
435m2·g-1.The pore volume of the modified zeolite molecular sieve is preferably 0.19~0.35cm3·g-1, more preferably 0.21~
0.33cm3·g-1, more preferably 0.23~0.31cm3·g-1, more preferably 0.25~0.29cm3·g-1.The modified zeolite
The aperture of molecular sieve is preferably 2.31~3.51nm, more preferably 2.51~3.31nm, more preferably 2.71~3.11nm, more excellent
Elect 2.81~3.01nm as.The sial atomic ratio of the modified zeolite molecular sieve is preferably 8.93~197.6, more preferably 20~
180, more preferably 50~150, more preferably 80~120.
Present invention also offers a kind of preparation method of modified zeolite molecular sieve solid acid catalyst, comprise the following steps：
1) after zeolite molecular sieve is mixed with acid, heating response, modified zeolite molecular sieve is obtained；
2) after being loaded using the salt containing active component on the modified zeolite molecular sieve that above-mentioned steps obtain, obtain
Modified zeolite molecular sieve solid acid catalyst.
In the above-mentioned preparation method of the present invention, range of choice, ratio and its optimum principle of the raw material, such as without especially note
It is bright, with the range of choice, ratio and its optimum principle of the material in aforementioned modified zeolite molecular sieve solid acid catalyst one by one
Corresponding, this is no longer going to repeat them.
After the present invention first mixes zeolite molecular sieve with acid, heating response, modified zeolite molecular sieve is obtained.
The present invention to it is described it is sour it is specifically chosen be not particularly limited, conventional modified used with well known to those skilled in the art
Acid, those skilled in the art can be selected and adjusted according to the condition of production, product requirement and quality requirement, the present invention
The acid preferably includes the one or more in nitric acid, hydrochloric acid, sulfuric acid, boric acid, oxalic acid, citric acid, more preferably nitric acid, salt
Acid, sulfuric acid, boric acid, oxalic acid or citric acid, more preferably nitric acid, hydrochloric acid, sulfuric acid or citric acid, most preferably nitric acid.
The temperature of the heating response is not particularly limited the present invention, with such reaction well known to those skilled in the art
Temperature, those skilled in the art can be selected and adjusted according to the condition of production, product requirement and quality requirement, this
The temperature for inventing the heating response is preferably 60~100 DEG C, more preferably 65~95 DEG C, more preferably 70~90 DEG C, more excellent
Elect 75~85 DEG C as.
The time of the heating response is not particularly limited the present invention, with such reaction well known to those skilled in the art
Time, those skilled in the art can be selected and adjusted according to applicable cases, product requirement and quality requirement, this
The time for inventing the heating response is preferably 5~15 hours, more preferably 7~13 hours, more preferably 9~11 hours.
Then the present invention is born using the salt containing active component on the modified zeolite molecular sieve that above-mentioned steps obtain
After load, modified zeolite molecular sieve solid acid catalyst is obtained.
The specifically chosen of soluble-salt containing active component is not particularly limited the present invention, with art technology
The soluble-salt of active component known to personnel, those skilled in the art can be according to the condition of production, product requirement and matter
Amount requirement is selected and adjusted, and the soluble-salt of the present invention containing active component includes the soluble chlorination of active component
Salt, the soluble nitrate of active component, the soluble acetate of active component, the soluble sulphate and activity of active component
One or more in the Soluble oxalate salt of component.
The concrete mode of the load is not particularly limited the present invention, with conventional load well known to those skilled in the art
Mode, those skilled in the art can be selected and adjusted, this hair according to the condition of production, product requirement and quality requirement
The method of the bright load preferably includes liquid-phase ion exchange, infusion process or solid liposome nanoparticle method, more preferably liquid phase from
Sub- exchange process.
The specific steps of the liquid-phase ion exchange are not particularly limited the present invention, with known to those skilled in the art
Conventional liquid phase ion-exchange mode of loading, those skilled in the art can according to the condition of production, product requirement and
Quality requirement is selected and adjusted, and the present invention further improves the performance of final products, optimize work to improve the degree of load
Skill route, when the method for the load is liquid-phase ion exchange, the preparation method is specially：
A) after zeolite molecular sieve is mixed with acid solution, heating response, modified zeolite molecular sieve is obtained；
B) modified zeolite molecular sieve, the soluble-salt containing active component and the water obtained above-mentioned steps mixes again
Afterwards, obtain exchanging modified molecular screen presoma；
C) the exchange modified molecular screen presoma for obtaining above-mentioned steps obtains modified zeolite molecular sieve and consolidated after roasting
Body acid catalyst.
After the present invention first mixes zeolite molecular sieve with acid solution, heating response, modified zeolite molecular sieve is obtained.
The concentration of the acid solution is not particularly limited the present invention, with conventional liquid phase well known to those skilled in the art from
The acid concentration of sub- exchange process, those skilled in the art can be selected according to the condition of production, product requirement and quality requirement
Select and adjust, the concentration of acid solution of the present invention is preferably 10wt%~30wt%, more preferably 12wt%~28wt%, more
Preferably 15wt%~25wt%.
The addition of the acid solution is not particularly limited the present invention, with conventional liquid phase well known to those skilled in the art
The acid solution addition of ion-exchange, those skilled in the art can want according to the condition of production, product requirement and quality
Ask and selected and adjusted, the mass ratio of zeolite molecular sieve and acid solution of the present invention is preferably 1：(20~100), more preferably
For 1：(30~90), more preferably 1：(40~80), more preferably 1：(50~70).
The present invention is in step a), the temperature of the heating response is not particularly limited, with known to those skilled in the art
Such reaction temperature, those skilled in the art can be selected according to the condition of production, product requirement and quality requirement
Select and adjust, the temperature of heating response of the present invention is preferably 60~100 DEG C, more preferably 65~95 DEG C, more preferably 70
~90 DEG C, more preferably 75~85 DEG C.
The present invention is in step a), the time of the heating response is not particularly limited, with known to those skilled in the art
Such reaction time, those skilled in the art can be selected according to the condition of production, product requirement and quality requirement
Select and adjust, the time of heating response of the present invention is preferably 5~15 hours, more preferably 7~13 hours, more preferably 9
~11 hours.
The present invention further improves the performance of final products, optimized process flow, the heating to improve the degree of load
Preferably also include post-processing step after reaction.
The detailed process of the post-processing step is not particularly limited the present invention, with it is well known to those skilled in the art this
The conventional post-processing step of class process, those skilled in the art can be according to the condition of production, product requirement and quality requirements
Selected and adjusted, post-processing step of the present invention preferably includes to stand, separates, be filtered, washed and dried in one kind
Or it is a variety of, more preferably stand, centrifuge, be filtered, washed and dried.The temperature of the drying is preferably 80~120 DEG C, more
Preferably 90~110 DEG C, more preferably 95~105 DEG C.The time of the drying is preferably 10~12 hours, more preferably 10.5
~11.5 hours, more preferably 10~11 hours.
Modified zeolite molecular sieve, the soluble-salt containing active component and the water that the present invention then obtains above-mentioned steps are again
After secondary mixing, obtain exchanging modified molecular screen presoma.
The present invention is in step b), the time mixed again is not particularly limited, with known to those skilled in the art
Such reaction typical mixing time, those skilled in the art can according to the condition of production, product requirement and quality will
To ask and selected and adjusted, the time of the present invention mixed again is preferably 6~24 hours, more preferably 10~20 hours,
More preferably 12~18 hours.
The present invention is in step b), the temperature mixed again is not particularly limited, with known to those skilled in the art
Such reaction temperature, those skilled in the art can be selected according to the condition of production, product requirement and quality requirement
Select and adjust, the temperature of the present invention mixed again is preferably 80~120 DEG C, more preferably 90~110 DEG C, more preferably 95
~105 DEG C.
For the present invention to improve the uniformity of above-mentioned steps, the soluble-salt more preferably containing active component adds deionization
In water, ultrasonic agitation (being preferably 30~60 minutes, more preferably 35~55 minutes, more preferably 40~50 minutes), add
Sour modified molecular screen is mixed again.
The present invention for improve load degree, further improve final products performance, optimized process flow, it is described again
Also include post-processing step again after mixing.
The detailed process of the post-processing step again is not particularly limited the present invention, with known to those skilled in the art
This class process conventional post-processing step, those skilled in the art can be according to the condition of production, product requirement and quality
It is required that being selected and being adjusted, post-processing step again of the present invention preferably includes to stand, separates, is filtered, washed and dried
In one or more, more preferably stand, filter, washing and dry.The washing preferably extremely contains the solvable of active component
Anion in property salt is not present.The temperature of the drying is preferably 100~120 DEG C, more preferably 105~115 DEG C, more
Preferably 100~110 DEG C.The time of the drying is preferably 10~12 hours, more preferably 10.5~11.5 hours, more preferably
For 10~11 hours.
The exchange modified molecular screen presoma that the present invention finally obtains above-mentioned steps obtains modified zeolite after roasting
Molecular sieve solid acid catalyst.
The time of the roasting is not particularly limited the present invention, with the normal of such reaction well known to those skilled in the art
Roasting time is advised, those skilled in the art can be selected and adjusted according to the condition of production, product requirement and quality requirement
Whole, the time of roasting of the present invention is preferably 10~12 hours, more preferably 10.5~11.5 hours, more preferably 10~11
Hour.
The temperature of the roasting is not particularly limited the present invention, with the roasting of such reaction well known to those skilled in the art
Temperature is burnt, those skilled in the art can be selected and adjusted according to the condition of production, product requirement and quality requirement, this
The temperature for inventing the roasting is preferably 400~700 DEG C, more preferably 450~650 DEG C, more preferably 500~600 DEG C.
The other conditions of the roasting are not particularly limited the present invention, with such reaction well known to those skilled in the art
Conventional roasting condition, those skilled in the art can be selected according to the condition of production, product requirement and quality requirement
And adjustment, roasting of the present invention are preferably to be calcined under air atmosphere.
Present invention also offers the modified zeolite molecular sieve solid acid catalyst described in above-mentioned technical proposal any one or
Application of the solid acid catalyst in catalyzed conversion biomass material lactic acid prepared by above-mentioned technical proposal any one.
The biomass material is not particularly limited the present invention, former with standard biologic matter well known to those skilled in the art
Material, those skilled in the art can be selected and adjusted according to the condition of production, product requirement and quality requirement, the present invention
The biomass material is preferably plant material, more preferably including one kind in leaf, stalk, peanut shell, cellulose and potato class
It is or a variety of.The potato class is more preferably cassava, is specifically as follows tapioca.
The detailed process of the application is not particularly limited the present invention, with this class process well known to those skilled in the art
, those skilled in the art can be selected and adjusted according to applicable cases, product requirement and quality requirement, institute of the present invention
The detailed process of application is stated, can be by taking tapioca as an example：
It is 1 in mass ratio by tapioca and modified zeolite molecular sieve solid acid catalyst, deionized water:0.03~0.3:
100 is well mixed, in 0.5~3.0MPa N2In atmosphere, 200~240 DEG C are reacted 30~60 minutes, after reaction terminates, use ice bath
Room temperature is rapidly cooled to, catalyst is centrifuged and reclaims, after reaction solution filtering with microporous membrane.
The invention provides a kind of modified zeolite molecular sieve solid acid catalyst and preparation method thereof, application, the present invention carries
A kind of modified zeolite molecular sieve solid acid catalyst is supplied, using specific active component, further with reference to specific nitric acid
Method of modifying and liquid-phase ion exchange, and its parameter, it is high, selective good with catalytic activity to be prepared, and catalyst is easy
In separation and recovery, it can be recycled and the advantage such as good cycling stability, and the method for preparing catalyst is simple, environmentally friendly
It is pollution-free.
Test result indicates that modified zeolite molecular sieve solid acid catalyst provided by the invention, for catalyzed conversion cassava
The catalytic activity of starch lactic acid is high, selective good, and catalyst is easily isolated and recycled, and good cycling stability, and can be complete
Full catalyzed conversion tapioca, lactic acid yield reach more than 65%.
In order to further illustrate the present invention, a kind of modified zeolite molecular sieve provided by the invention is consolidated with reference to embodiments
Body acid catalyst and preparation method thereof, using being described in detail, but it is to be understood that these embodiments are with skill of the present invention
Implemented under premised on art scheme, give detailed embodiment and specific operating process, be simply further explanation
The features and advantages of the present invention, rather than limiting to the claimed invention, protection scope of the present invention are also not necessarily limited to following
Embodiment.
Embodiment 1
1st, sour modified zsm-5 zeolite is prepared
The commercial H-ZSM-5 zeolite molecular sieves (being purchased from Tianjin Nankai university catalyst plant) of 2g are weighed in 98g 20wt%'s
In salpeter solution, stirred 6 hours at 100 DEG C, stand, centrifuge, being washed with deionized to neutrality, 110 DEG C of dryings 12 are small
When, obtain the modified ZSM-5 molecular sieve of acid.
2nd, solid acid catalyst is prepared
Using ion-exchange, it is 20wt% by the load capacity of scandium ion, 0.8415g scandium chlorides is added to 50mL deionizations
In water, it is stirred by ultrasonic 30 minutes, adds 1g acid modified molecular screens, stirred 6 hours at 80 DEG C, stand 12 hours, filters, spend
Ion water washing exists to without chlorion, is calcined 6 hours at 110 DEG C of dryings 12 hours, 550 DEG C, is prepared into scandium ion exchange
ZSM-5 solid acid catalysts.
The catalyst prepared to the embodiment of the present invention 1 detects, and wherein specific surface area is 400.6m2·g-1, pore volume
For 0.32cm3·g-1, aperture 3.35nm, silicon and al atomic ratio are 131.4.
Embodiment 2
In the present embodiment, the commercial ZSM-5 molecular sieves of 2g are scattered in the aqueous solution of nitric acid that 98g mass fractions are 20%
In, the ZSM-5 molecular sieve suspension that mass fraction is 2% is configured to, is stirred 2 hours at 100 DEG C, other steps and embodiment 1
It is identical, it is prepared into solid acid catalyst.
The catalyst prepared to the embodiment of the present invention 2 detects, and wherein specific surface area is 415.9m2·g-1, pore volume
For 0.35cm3·g-1, aperture 3.32nm, silicon and al atomic ratio are 114.7.
Embodiment 3
In the present embodiment, the commercial ZSM-5 molecular sieves of 2g are scattered in the aqueous solution of nitric acid that 98g mass fractions are 20%
In, the ZSM-5 molecular sieve suspension that mass fraction is 2% is configured to, is stirred 4 hours at 100 DEG C, other steps and embodiment 1
It is identical, it is prepared into solid acid catalyst.
The catalyst prepared to the embodiment of the present invention 3 detects, and wherein specific surface area is 408.5m2·g-1, pore volume
For 0.34cm3·g-1, aperture 3.33nm, silicon and al atomic ratio are 125.8.
Embodiment 4
In the present embodiment, the commercial ZSM-5 molecular sieves of 2g are scattered in the aqueous solution of nitric acid that 98g mass fractions are 20%
In, the ZSM-5 molecular sieve suspension that mass fraction is 2% is configured to, is stirred 10 hours at 100 DEG C, other steps and embodiment 1
It is identical, it is prepared into solid acid catalyst.
The catalyst prepared to the embodiment of the present invention 4 detects, and wherein specific surface area is 375.8m2.g-1, pore volume be
0.33cm3·g-1, aperture 3.51nm, silicon and al atomic ratio are 197.6.
Embodiment 5
In the present embodiment, using ion-exchange, it is 10wt% by the load capacity of scandium ion, 0.3740g scandium chlorides is added
Enter into 50mL deionized waters, be stirred by ultrasonic 30 minutes, add the unmodified ZSM-5 molecular sieves of 1g, stirring 6 is small at 80 DEG C
When, other steps are same as Example 1, are prepared into solid acid catalyst.
The catalyst prepared to the embodiment of the present invention 5 detects, and wherein specific surface area is 448.9m2·g-1, pore volume
For 0.26cm3·g-1, aperture 2.31nm, silicon and al atomic ratio are 10.1.
Embodiment 6
In the present embodiment, using ion-exchange, it is 20wt% by the load capacity of scandium ion, 0.8415g scandium chlorides is added
Enter into 50mL deionized waters, be stirred by ultrasonic 30 minutes, add the unmodified ZSM-5 molecular sieves of 1g, stirring 6 is small at 80 DEG C
When, other steps are same as Example 1, are prepared into solid acid catalyst.
The catalyst prepared to the embodiment of the present invention 6 detects, and wherein specific surface area is 394.8m2·g-1, pore volume
For 0.24cm3·g-1, aperture 2.39nm, silicon and al atomic ratio are 9.6.
Embodiment 7
In the present embodiment, using ion-exchange, it is 30wt% by the load capacity of scandium ion, 1.4425g scandium chlorides is added
Enter into 50mL deionized waters, be stirred by ultrasonic 30 minutes, add the unmodified ZSM-5 molecular sieves of 1g, stirring 6 is small at 80 DEG C
When, other steps are same as Example 1, are prepared into solid acid catalyst.
The catalyst prepared to the embodiment of the present invention 7 detects, and wherein specific surface area is 352.5m2·g-1, pore volume
For 0.23cm3·g-1, aperture 2.68nm, sial atomic ratio be 8.9.
Embodiment 8
In the present embodiment, using ion-exchange, it is 20wt% by the load capacity of scandium, 0.8415g scandium chlorides is added to
In 50mL deionized waters, it is stirred by ultrasonic 30 minutes, adds ZSM-5 molecular sieve modified in embodiment 1,24 are stirred at 100 DEG C
Hour, other steps are same as Example 1, are prepared into solid acid catalyst.
The catalyst prepared to the embodiment of the present invention 8 detects, and wherein specific surface area is 320.9m2·g-1, pore volume
For 0.23cm3·g-1, aperture 2.84nm.
Embodiment 9
It is 20wt% by the load capacity of indium ion using ion-exchange, by the anhydrous chlorinations of 0.4816g in the present embodiment
Indium is added in 50mL deionized waters, is stirred by ultrasonic 30 minutes, adds in embodiment 1 modified ZSM-5 molecular sieve, at 80 DEG C
Stirring 6 hours, other steps are same as Example 1, are prepared into solid acid catalyst.
Embodiment 10
It is 20wt% by the load capacity of ytterbium ion, by 0.4298g chloride hydrates using ion-exchange in the present embodiment
Ytterbium is added in 50mL deionized waters, is stirred by ultrasonic 30 minutes, is added modified zsm-5 zeolite in embodiment 1, stirred at 80 DEG C
Mix 6 hours, other steps are same as Example 1, are prepared into solid acid catalyst.
Embodiment 11
It is 20wt% by the load capacity of chromium ion using ion-exchange in the present embodiment, by the water chlorinations of 1.2812g six
Chromium is added in 50mL deionized waters, is stirred by ultrasonic 30 minutes, adds in embodiment 1 modified ZSM-5 molecular sieve, at 80 DEG C
Stirring 6 hours, other steps are same as Example 1, are prepared into solid acid catalyst.
Embodiment 12
In the present embodiment, using ion-exchange, it is 20wt% by the load capacity of niobium ion, 0.5403g niobium chlorides is added
Enter into 50mL deionized waters, be stirred by ultrasonic 30 minutes, add ZSM-5 molecular sieve modified in embodiment 1, stirred at 80 DEG C
6 hours, other steps were same as Example 1, are prepared into solid acid catalyst.
Embodiment 13
It is 20wt% by the load capacity of holmium ion, by 0.4676g chloride hydrates using ion-exchange in the present embodiment
Holmium is added in 50mL deionized waters, is stirred by ultrasonic 30 minutes, adds in embodiment 1 modified ZSM-5 molecular sieve, at 80 DEG C
Stirring 6 hours, other steps are same as Example 1, are prepared into solid acid catalyst.
Embodiment 14
In the present embodiment, using ion-exchange, it is 20wt% by the load capacity of praseodymium ion, 0.4387g praseodymium chlorides is added
Enter into 50mL deionized waters, be stirred by ultrasonic 30 minutes, add ZSM-5 molecular sieve modified in embodiment 1, stirred at 80 DEG C
6 hours, other steps were same as Example 1, are prepared into solid acid catalyst.
Embodiment 15
Using infusion process, it is 20wt% by the load capacity of scandium ion, 0.8415g scandium chlorides is dissolved in 50mL deionized waters
In, ZSM-5 zeolite molecular sieves of the 1g without nitric acid treatment is added, at room temperature dipping 6 hours, still aging 12 hours,
It is calcined 6 hours at 110 DEG C of dryings 12 hours, 550 DEG C, the scandium ZSM-5 solid acid catalysts of infusion process is prepared.
The catalyst prepared to the embodiment of the present invention 15 detects, and wherein specific surface area is 328.6m2·g-1, pore volume
For 0.19cm3·g-1, aperture 2.41nm, silicon and al atomic ratio are 9.9.
Embodiment 16
Using solid liposome nanoparticle method, ZSM-5 is first subjected to dealumination treatment with 250mL10M salpeter solution, at 100 DEG C
Stirring 20 hours, stand, be washed with deionized to neutrality, dry, obtain the ZSM-5 molecular sieve of complete dealuminzation.Then by 1g
ZSM-5 molecular sieve after dealuminzation is ground 30 minutes with 0.8415g scandium chloride solids, is finally calcined 6 hours at 550 DEG C,
The scandium ZSM-5 solid acid catalysts of solid liposome nanoparticle are prepared.
The catalyst prepared to the embodiment of the present invention 5 detects, and wherein specific surface area is 436.1m2·g-1, pore volume
For 0.27cm3·g-1, aperture 2.50nm.
Embodiment 17
Solid acid catalyst prepared by embodiment 1~16 is applied in catalyzed conversion tapioca lactic acid, had
Body application method is：
Weigh 0.30g tapiocas, 0.05g above-described embodiments prepare solid acid catalyst, 25mL water it is stainless in 35mL
In steel autoclave, the air that is passed through at room temperature in nitrogen displacement autoclave in triplicate, then is passed through 2MPa nitrogen
Gas, under 600 revs/min of stirring conditions, 200 DEG C are reacted 60 minutes, and reaction centrifuges catalyst after terminating, and reaction solution is used
After 0.22 μm of filtering with microporous membrane, with the yield of high performance liquid chromatography measure and calculation lactic acid, 1 the results are shown in Table.Table 1 is real for the present invention
Apply lactic acid production of the modified zeolite molecular sieve solid acid catalyst of the preparation of example 1~16 in catalyzed conversion tapioca lactic acid
Rate.
Table 1
The sour modified zeolite molecular sieve solid acid catalyst that active component is loaded with the embodiment of the present invention is circulated
Performance detection, by taking embodiment 1 as an example, after recycling 5 times, the yield of lactic acid is 65.3；Remaining embodiment rate of descent is 1%
~2%.
Above to a kind of modified zeolite molecular sieve solid acid catalyst provided by the invention and preparation method thereof, in biomass
The application that catalytic material is converted in lactic acid processed is described in detail, principle of the specific case to the present invention used herein
And embodiment is set forth, the explanation of above example is only intended to help method and its core think of for understanding the present invention
Think, including best mode, and also cause any person skilled in the art to put into practice the present invention, including manufacture and use
Any device or system, and implement the method for any combination.It should be pointed out that come for those skilled in the art
Say, under the premise without departing from the principles of the invention, some improvement and modification can also be carried out to the present invention, these are improved and modification
Also fall into the protection domain of the claims in the present invention.The scope of patent protection of the present invention is defined by the claims, and can
Including those skilled in the art it is conceivable that other embodiment.If these other embodiments, which have, is similar to claim text
The structural element of word statement, or if they include wanting with equivalent structure of the character express without essence difference of claim
Element, then these other embodiments should also include within the scope of the claims.
Claims (10)
1. a kind of modified zeolite molecular sieve solid acid catalyst, it is characterised in that including modified zeolite molecular sieve and be supported on institute
State the active component on modified zeolite molecular sieve；
The active component include chromium ion, praseodymium ion, lutetium ion, niobium ion, holmium ion, thulium ion, gadolinium ion, samarium ion,
One or more in ruthenium ion, europium ion, ytterbium ion, neodymium ion, dysprosium ion, indium ion and scandium ion.
2. solid acid catalyst according to claim 1, it is characterised in that the load capacity of the active component is 10wt%
~30wt%；
The modified zeolite molecular sieve is sour modified zeolite molecular sieve；
The zeolite molecular sieve includes the one or more in type ZSM 5 molecular sieve, beta molecular sieve and HY type molecular sieves.
3. solid acid catalyst according to claim 1, it is characterised in that the specific surface area of the modified zeolite molecular sieve
For 328.6~448.9m2·g-1；
The pore volume of the modified zeolite molecular sieve is 0.19~0.35cm3·g-1；
The aperture of the modified zeolite molecular sieve is 2.31~3.51nm；
The sial atomic ratio of the modified zeolite molecular sieve is 8.93~197.6.
4. a kind of preparation method of modified zeolite molecular sieve solid acid catalyst, it is characterised in that comprise the following steps：
1) after zeolite molecular sieve is mixed with acid, heating response, modified zeolite molecular sieve is obtained；
2) after being loaded using the salt containing active component on the modified zeolite molecular sieve that above-mentioned steps obtain, it is modified
Zeolite molecular sieve solid acid catalyst.
5. preparation method according to claim 1, it is characterised in that the acid includes nitric acid, hydrochloric acid, sulfuric acid, boric acid, grass
One or more in acid, citric acid；
The temperature of the heating response is 60~100 DEG C；
The time of the heating response is 5~15 hours.
6. preparation method according to claim 1, it is characterised in that the method for the load includes ion exchange in solution
Method, infusion process or solid liposome nanoparticle method；
When the method for the load is liquid-phase ion exchange, the preparation method is specially：
A) after zeolite molecular sieve is mixed with acid solution, heating response, modified zeolite molecular sieve is obtained；
B) after modified zeolite molecular sieve, the soluble-salt containing active component and the water obtained above-mentioned steps mixes again, obtain
To exchange modified molecular screen presoma；
C) the exchange modified molecular screen presoma for obtaining above-mentioned steps obtains modified zeolite molecular sieve solid acid after roasting
Catalyst.
7. preparation method according to claim 1, it is characterised in that the concentration of the acid solution be 10wt%~
30wt%；
The mass ratio of the zeolite molecular sieve and acid solution is 1：(20~100).
8. preparation method according to claim 1, it is characterised in that also include post-processing step after the heating response；
The time mixed again is 6~24 hours；
The temperature mixed again is 80~120 DEG C；
Also include post-processing step again after the mixing again；
The post-processing step includes the one or more in standing, separate, being filtered, washed and dried.
9. preparation method according to claim 1, it is characterised in that the temperature of the roasting is 400~700 DEG C；
The time of the roasting is 10~12 hours.
10. the modified zeolite molecular sieve solid acid catalyst or claim 4~9 described in claims 1 to 3 any one are any
Application of the solid acid catalyst in catalyzed conversion biomass material lactic acid prepared by one.
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| CN111807947A (en) * | 2020-07-24 | 2020-10-23 | 福建师范大学泉港石化研究院 | Method for preparing lactic acid by catalytic conversion of carbohydrate |
| CN115301284A (en) * | 2022-08-05 | 2022-11-08 | 同济大学 | Modified Beta molecular sieve for catalytically converting biomass into lactic acid and preparation method and application thereof |
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| CN115301284A (en) * | 2022-08-05 | 2022-11-08 | 同济大学 | Modified Beta molecular sieve for catalytically converting biomass into lactic acid and preparation method and application thereof |
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