CN114367302A - Preparation method and application of catalyst for preparing hydrocyanic acid by ammoxidation of methanol - Google Patents
Preparation method and application of catalyst for preparing hydrocyanic acid by ammoxidation of methanol Download PDFInfo
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- CN114367302A CN114367302A CN202111632115.9A CN202111632115A CN114367302A CN 114367302 A CN114367302 A CN 114367302A CN 202111632115 A CN202111632115 A CN 202111632115A CN 114367302 A CN114367302 A CN 114367302A
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- catalyst
- solid
- methanol
- crystallization
- hydrocyanic acid
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 57
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000003054 catalyst Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000007787 solid Substances 0.000 claims abstract description 24
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000005470 impregnation Methods 0.000 claims abstract description 7
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 5
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000002425 crystallisation Methods 0.000 claims description 26
- 230000008025 crystallization Effects 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 18
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 239000012752 auxiliary agent Substances 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 239000011733 molybdenum Substances 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 150000002603 lanthanum Chemical class 0.000 claims description 4
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 4
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 3
- 229940010552 ammonium molybdate Drugs 0.000 claims description 3
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 3
- 239000011609 ammonium molybdate Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-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
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- WFLYOQCSIHENTM-UHFFFAOYSA-N molybdenum(4+) tetranitrate Chemical compound [N+](=O)([O-])[O-].[Mo+4].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] WFLYOQCSIHENTM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 230000001502 supplementing effect Effects 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 150000002751 molybdenum Chemical class 0.000 claims 3
- 238000001354 calcination Methods 0.000 claims 1
- 239000004615 ingredient Substances 0.000 claims 1
- VQEHIYWBGOJJDM-UHFFFAOYSA-H lanthanum(3+);trisulfate Chemical compound [La+3].[La+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VQEHIYWBGOJJDM-UHFFFAOYSA-H 0.000 claims 1
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims 1
- ICYJJTNLBFMCOZ-UHFFFAOYSA-J molybdenum(4+);disulfate Chemical compound [Mo+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ICYJJTNLBFMCOZ-UHFFFAOYSA-J 0.000 claims 1
- 238000002791 soaking Methods 0.000 claims 1
- LTYRAPJYLUPLCI-UHFFFAOYSA-N glycolonitrile Chemical compound OCC#N LTYRAPJYLUPLCI-UHFFFAOYSA-N 0.000 abstract description 8
- 239000006227 byproduct Substances 0.000 abstract description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 abstract 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 24
- 238000011156 evaluation Methods 0.000 description 8
- 238000005406 washing Methods 0.000 description 6
- -1 molybdenum metals Chemical class 0.000 description 5
- 238000001914 filtration Methods 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 238000000643 oven drying Methods 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- CBHOOMGKXCMKIR-UHFFFAOYSA-N azane;methanol Chemical compound N.OC CBHOOMGKXCMKIR-UHFFFAOYSA-N 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 231100000481 chemical toxicant Toxicity 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- DSMZRNNAYQIMOM-UHFFFAOYSA-N iron molybdenum Chemical compound [Fe].[Fe].[Mo] DSMZRNNAYQIMOM-UHFFFAOYSA-N 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229930182817 methionine Natural products 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 239000010457 zeolite Substances 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
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0341—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- B01J35/50—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C3/00—Cyanogen; Compounds thereof
- C01C3/02—Preparation, separation or purification of hydrogen cyanide
- C01C3/0208—Preparation in gaseous phase
- C01C3/0241—Preparation in gaseous phase from alcohols or aldehydes
-
- 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
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention relates to a preparation method of a novel catalyst for preparing hydrocyanic acid by ammoxidation of methanol. The preparation method comprises the following steps: solid S-1 is synthesized first, and then lanthanum molybdate is encapsulated inside the hollow S-1 by a method of 'impregnation first and post treatment'. Finally, centrifuging, drying and roasting. The prepared hollow S-1 zeolite-packaged metal catalyst has good catalytic performance in the preparation of hydrocyanic acid by methanol ammoxidation, the yield of the hydrocyanic acid is over 90 percent, the total amount of byproducts such as formaldehyde, hydroxy acetonitrile and the like is less than 0.05 percent, and the service life of the catalyst can reach over 2000 h.
Description
Technical Field
The invention relates to a preparation method of a novel catalyst for preparing hydrocyanic acid by ammoxidation of methanol, and the catalyst is used for preparing the hydrocyanic acid by ammoxidation of the methanol.
Background
Hydrocyanic acid is an important chemical raw material, is mainly used for producing chemical products such as adiponitrile, MMA, methionine and the like, and has wide application. However, hydrocyanic acid is a highly toxic chemical and cannot be transported. Therefore, the demand for hydrocyanic acid is self-sufficient. At present, hydrocyanic acid is mainly sourced from several types in the society, including an acrylonitrile byproduct, a methane method and a methanol method. With the continuous development of acrylonitrile catalysts, the yield of hydrocyanic acid is lower and lower. The methane method requires the use of expensive noble metal catalysts, the reaction temperature exceeds 1000 ℃, and the yield is low, so that the economy is poor. The methanol method is an economic hydrocyanic acid production method, methanol, ammonia gas and air are used as raw materials, hydrocyanic acid is produced under the action of a catalyst, the production condition is mild, the yield of hydrocyanic acid is high, and the method has the advantage of higher cost.
The mainstream catalyst for producing hydrocyanic acid by a methanol method is an iron and molybdenum bimetallic catalyst. Excessive ammonia gas in raw materials needs to be recovered by matching with an ammonium sulfate system, however, the process has a defect that formaldehyde is inevitably generated in the reaction due to the existence of iron and molybdenum metals, the formaldehyde reacts with hydrocyanic acid to generate substances such as hydroxyl acetonitrile and the like, and the macromolecular substances are easy to polymerize to block pipelines and filters. As the reaction for generating the hydroxyacetonitrile is a reversible reaction, a large amount of hydrocyanic acid can be released when the filter is cleaned, and the method has great potential safety hazard. Meanwhile, the frequent blockage brings great challenges to the stable operation of the device.
Disclosure of Invention
Aiming at the problems, the invention provides a preparation method of a methanol ammonia oxidation hydrocyanic acid catalyst, in particular to a preparation method of an S-1 packaging metal catalyst which is suitable for methanol ammonia oxidation and has a hollow structure. The catalyst maintains high hydrocyanic acid yield, and simultaneously, the total formaldehyde byproduct yield is lower than 0.05 percent and is far superior to other industrialized catalysts.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
(1) preparing solid S-1 by adopting a static crystallization method: mixing a certain amount of TPAOH (tetrapropylammonium hydroxide), TEOS (tetraethyl orthosilicate) and water according to a certain proportion, and stirring to obtain a clear solution; stirring at a certain temperature to remove alcohol and supplement water; then placing the mixture into a crystallization kettle, crystallizing at high temperature, and finally washing and roasting to obtain solid S-1;
(2) preparing a mixed solution of ammonium salt, lanthanum salt and an auxiliary agent, and impregnating the metal on the surface and in the pore channels of the zeolite in an impregnation mode. Drying after the impregnation is finished to obtain solid S-1 loaded with metal;
(3) and (3) putting the material prepared in the step (2) into a template solution again, and crystallizing to obtain the catalyst.
In the invention, in the step (1), the solid S-1 is prepared by adopting a hydrothermal synthesis method, firstly, a precursor is prepared, a certain amount of TPAOH is firstly taken, added into a certain amount of water, stirred and dissolved. After the dissolution was completed, TEOS was added and stirring was continued. Ensuring that the mass ratio of TPAOH to TEOS to H is2O is x, y and 1, wherein x is 0.02-0.1, and y is 0.01-0.1. Preferably, x is 0.04 to 0.09 and y is 0.03 to 0.08. After the addition is complete, the temperature is raised to 60-100 ℃, and stirring is continued for 0.5-3h, preferably 1-2h after sealing. And then opening the chamber to remove the alcohol for 20-40min, and then supplementing water to the original volume to obtain the precursor.
In the invention, after the precursor preparation in the step (1) is finished, static crystallization is started. Crystallizing by using a crystallization kettle with a polytetrafluoroethylene lining, wherein the crystallization temperature is 160-250 ℃, preferably 180-220 ℃, and the crystallization time is 24-72h, preferably 36-48 h. After crystallization is finished, taking turbid liquid in the kettle, centrifugally washing to be neutral, drying at 80-120 ℃ for 4-8h, and roasting at 380-540 ℃ for 4-10h to obtain solid S-1.
In the invention, the high-efficiency catalyst of the S-1 encapsulated metal with a hollow structure is obtained by adopting a mode of first impregnation and then treatment. The invention adopts a mode of excessive impregnation. The impregnating solution is a mixed solution of a plurality of metal salt solutions. The main catalyst components are lanthanum and molybdenum; the catalyst promoter is the key for reducing the yield of formaldehyde, and the catalyst promoter is one or more of iron, bismuth, cobalt, nickel, phosphorus, copper, zinc and iridium. Firstly, preparing a salt solution of lanthanum and molybdenum, wherein the mass fraction of molybdenum is 2-20 wt%, preferably 5-15 wt%. The mass fraction of lanthanum is 2 to 10 wt.%, preferably 3 to 8 wt.%. Then adding an auxiliary agent, wherein the mass fraction of the auxiliary agent is 1-5 wt%. Heating to 20-70 deg.C after dissolving completely, stirring for 10-40min, and adding solid S-1. Adding solid S-1 in an amount of 2-20 wt%, preferably 2-5 wt%, of the total solution for 60-120min, filtering, washing, and oven drying.
In the invention, step (3) adopts a secondary crystallization mode to obtain Hol S-1 with a hollow structure. And adding the solid S-1 loaded with the metal into a TPAOH solution with the mass fraction of 10-25 wt%. The mass ratio of the metal-loaded solid S-1 to the TPAOH solution is 0.1-1:1, preferably 0.2-0.8: 1. The crystallization temperature is 120-210 ℃, preferably 170-200 ℃. The rotation rate is 5-20r/min, and the crystallization is 24-72 h. Drying after the completion, and roasting at 380-540 ℃ for 4-10h to obtain the catalyst.
In the present invention, the catalyst was evaluated using a molten salt apparatus. The temperature of the molten salt is 300-400 ℃, and is preferably 320-380 ℃. The reaction raw materials are methanol, ammonia gas and air, and the feeding molar ratio is 1: x: y, wherein X is from 0.5 to 5, preferably from 1 to 2.5, and y is from 80 to 100, preferably from 90 to 96. The reaction raw materials enter a reaction tube after being preheated, and the preheating temperature is 100-250 ℃. 50mL of catalyst is filled, and the total volume space velocity is 1000--1. Preferably 1500--1. The reaction gas is analyzed by gas chromatography, wherein the yield of hydrocyanic acid is more than 90 percent, the yield of formaldehyde and hydroxy acetonitrile is less than 0.05 percent, and the service life of the catalyst reaches more than 2000 h.
The specific implementation mode is as follows:
the following examples are intended to illustrate the invention, which is not limited to the scope of the examples, but also includes any other modifications within the scope of the claims of the invention.
The gas chromatography conditions used in the examples of the present invention were: agilent HP-INNOWAX chromatographic column, injection port temperature: 280 ℃; detector temperature: 240 ℃; h2Flow rate: 35 ml/min; air flow rate: 350 ml/min.
Example 1
80g of water is taken into a beaker, 4.514g of TPAOH is added and stirred, then 4.6g of TEOS is added, the temperature is raised to 80 ℃, and the mixture is sealed and stirred for 65 min. Then open, remove alcohol for 30min, and replenish water to the original volume. Then pouring the mixture into a 100mL crystallization kettle with a polytetrafluoroethylene lining, and crystallizing the mixture for 36 hours at 180 ℃. And after the completion, washing the obtained turbid liquid to be neutral, drying the turbid liquid for 6h at 100 ℃, and roasting the turbid liquid for 4h at 540 ℃ to obtain solid S-1.
100g of water was taken, and 6g of ammonium molybdate, 3g of lanthanum nitrate and 1.5g of ferric nitrate were added. After stirring at 50 ℃ for 30min, 2.5g of solid S-1 were added to the metal solution. Adsorbing for 60min, filtering, and oven drying.
10g of TPAOH solution with the mass fraction of 10% is prepared, and 2g of S-1 loaded with metal is added. After being stirred evenly, the mixture is poured into a crystallization kettle, crystallized for 24 hours at the speed of 10r/min at the temperature of 170 ℃, and roasted for 6 hours at the temperature of 540 ℃ after the crystallization is finished, thus obtaining the catalyst.
50mL of catalyst is loaded into a reaction tube, the temperature of a catalyst bed layer is heated to 340 ℃, and the material is preheated at 120 ℃ and then contacts with the catalyst to react. The molar ratio of methanol, ammonia and air fed at the reaction temperature is 1:1.1: 90. The total airspeed is 1500h-1. The evaluation results were as follows:
| evaluation time | Hydrocyanic acid yield | Total yield of formaldehyde and hydroxyacetonitrile |
| 1h | 91.3％ | 0.0023％ |
| 100h | 92.7％ | 0.0045％ |
| 500h | 91.5％ | 0.0047％ |
| 1000h | 90.9％ | 0.0031％ |
| 1500h | 92.3％ | 0.0029％ |
| 2000h | 90.7％ | 0.0049％ |
Example 2
80g of water is taken into a beaker, 3.5g of TPAOH is added and stirred, then 2.75g of TEOS is added, the temperature is raised to 80 ℃, and the mixture is sealed and stirred for 120 min. Then open, remove alcohol for 30min, and replenish water to the original volume. Then pouring the mixture into a 100mL crystallization kettle with a polytetrafluoroethylene lining, and crystallizing the mixture for 48 hours at 210 ℃. And after the completion, washing the obtained turbid liquid to be neutral, drying the turbid liquid for 6h at 100 ℃, and roasting the turbid liquid for 4h at 540 ℃ to obtain solid S-1.
100g of water is taken, and 14g of molybdenum nitrate, 8g of lanthanum nitrate, 0.7g of ferric nitrate and 0.8g of cupric nitrate are added. After stirring at 50 ℃ for 30min, 7.5g of solid S-1 were added to the metal solution. Adsorbing for 90min, filtering, and oven drying.
10g of a 20% TPAOH solution was prepared, and 8g of metal-loaded S-1 was added. After being stirred evenly, the mixture is poured into a crystallization kettle, crystallized for 24 hours at the speed of 2r/min at the temperature of 200 ℃, and roasted for 6 hours at the temperature of 540 ℃ after the crystallization is finished, thus obtaining the catalyst.
50mL of catalyst is loaded into a reaction tube, the temperature of a catalyst bed layer is heated to 390 ℃, and the material is preheated at 230 ℃ and then contacts with the catalyst to react. The molar ratio of the fed methanol, the ammonia gas and the air is 1:1.4:95, and the total space velocity is 2000h-1。
The evaluation results were as follows:
| evaluation time | Hydrocyanic acid yield | Total yield of formaldehyde and hydroxyacetonitrile |
| 1h | 92.9％ | 0.0015％ |
| 100h | 91.8％ | 0.0037％ |
| 500h | 90.9％ | 0.0029％ |
| 1000h | 95.3％ | 0.0034％ |
| 1500h | 95.1％ | 0.0027％ |
| 2000h | 94.7％ | 0.0035％ |
Example 3
80g of water is taken into a beaker, 7.3g of TPAOH is added and stirred, then 6.4g of TEOS is added, the temperature is raised to 80 ℃, and the mixture is sealed and stirred for 80 min. Then open, remove alcohol for 30min, and replenish water to the original volume. Then pouring the mixture into a 100mL crystallization kettle with a polytetrafluoroethylene lining, and crystallizing the mixture for 45 hours at 190 ℃. And after the completion, washing the obtained turbid liquid to be neutral, drying the turbid liquid for 6h at 100 ℃, and roasting the turbid liquid for 4h at 540 ℃ to obtain solid S-1.
100g of water is taken, 10g of ammonium molybdate, 5.4g of lanthanum nitrate, 3.8g of zinc nitrate and 2.1g of cobalt nitrate are added. After stirring at 50 ℃ for 30min, 5g of solid S-1 were added to the metal solution. Adsorbing for 120min, filtering, and oven drying.
10g of TPAOH solution with the mass fraction of 15% is prepared, and 6g of S-1 loaded with metal is added. After being stirred evenly, the mixture is poured into a crystallization kettle, crystallized for 34 hours at the speed of 5r/min at the temperature of 190 ℃, and roasted for 6 hours at the temperature of 540 ℃ after the crystallization is finished, thus obtaining the catalyst.
50mL of catalyst is loaded into a reaction tube, the temperature of a catalyst bed layer is heated to 390 ℃, and the material is preheated at 200 ℃ and then contacts with the catalyst to react. The molar ratio of methanol, ammonia and air fed is 1:1.25: 92.5. The total airspeed is 2500h-1. The evaluation results were as follows:
| evaluation time | Hydrocyanic acid yield | Total yield of formaldehyde and hydroxyacetonitrile |
| 1h | 90.6％ | 0.0019％ |
| 100h | 91.4％ | 0.0005％ |
| 500h | 91.7％ | 0.0015％ |
| 1000h | 92.1％ | 0.0014％ |
| 1500h | 92.6％ | 0.0029％ |
| 2000h | 90.5％ | 0.0027％ |
Comparative example:
50mL of a conventional commercial iron-molybdenum-based methanol ammoxidation catalyst was purchased from Zibotian Chengtai chemical company under the evaluation conditions in example 1, and the results were as follows:
| evaluation time | Hydrocyanic acid yield | Total yield of formaldehyde and hydroxyacetonitrile |
| 1h | 85.1％ | 0.0523％ |
| 100h | 86.7％ | 0.0826％ |
| 500h | 82.6％ | 0.0437％ |
| 1000h | 80.7％ | 0.0681％ |
| 1500h | 78.5％ | 0.0924％ |
| 2000h | 75.8％ | 0.1052％ |
Claims (10)
1. A preparation method of a catalyst for preparing hydrocyanic acid by ammoxidation of methanol is characterized by comprising the following steps:
(1) TPAOH tetrapropylammonium hydroxide, TEOS ethyl orthosilicate and water are mixed according to a certain proportion and stirred to obtain a clear solution, the clear solution is stirred at a certain temperature to remove alcohol, water is supplemented to obtain a precursor, then the precursor is crystallized at a high temperature, and finally the precursor is washed and roasted to obtain solid S-1;
(2) preparing a mixed solution of molybdenum salt, lanthanum salt and an auxiliary agent, impregnating the mixed solution on the surface of the solid S-1 and inside the pore channel in an impregnation mode, and drying after impregnation to obtain the solid S-1 loaded with metal;
(3) and (3) placing the material prepared in the step (2) in a template solution again, and crystallizing to obtain the catalyst.
2. The method of claim 1, wherein: the ingredients are as follows according to mass ratio:
TPAOH:TEOS:H2o is x, y and 1, wherein x is 0.02-0.1, and y is 0.01-0.1.
3. The method according to claim 1 or 2, characterized in that: and (2) stirring in the step (1) in a water bath at 60-100 ℃ in a sealed environment for 0.5-3h, after stirring, removing alcohol in an open way for 20-40min, and then supplementing water to the original volume to obtain the precursor.
4. The method according to any one of claims 1-3, wherein: in the step (1), the obtained precursor is poured into a crystallization kettle, the crystallization temperature is 160-250 ℃, the crystallization time is 24-72h, and standing crystallization is carried out; and/or after crystallization is finished, centrifuging turbid liquid in the kettle, drying for 4-8h at 80-120 ℃, and then roasting for 4-10h at 380-540 ℃ to obtain solid S-1.
5. The method according to any one of claims 1-4, wherein: in the step (2), the mass fraction of molybdenum salt in the prepared mixed solution of molybdenum, lanthanum and auxiliary agent is 2-20 wt%, and the mass fraction of lanthanum salt is 2-10 wt%; wherein, the molybdenum salt is selected from one of ammonium molybdate, molybdenum nitrate and molybdenum sulfate, and the lanthanum salt is selected from one of lanthanum nitrate, lanthanum chloride and lanthanum sulfate; and/or the auxiliary agent is metal salt, the auxiliary agent metal is one or more of iron, bismuth, cobalt, nickel, phosphorus, copper, zinc and iridium, and the mass fraction of the auxiliary agent is 1-5 wt%.
6. The method according to any one of claims 1-5, wherein: in the step (2), the mixed solution is heated to 20-70 ℃, and solid S-1 is added after stirring for 10-40min, wherein the solid S-1 accounts for 2-20 wt% of the solution; the soaking time is 60-120 min.
7. The method according to any one of claims 1-6, wherein: in the step (3), the solid S-1 loaded with metal is added into a TPAOH solution with the weight percent of 10-25, the mass ratio of the solid S-1 loaded with metal to the TPAOH solution is 0.1-1:1, and/or the crystallization temperature is 120-210 ℃, the rotation rate is 5-20r/min, the crystallization time is 24-72h, and/or the calcination is carried out at 380-540 ℃ for 4-10h, so as to obtain the catalyst.
8. Use of a catalyst prepared according to the method of any one of claims 1-7 as a catalyst for the ammoxidation of methanol to hydrocyanic acid.
9. Use according to claim 8, characterized in that: mixing and preheating methanol, ammonia gas and air according to a certain proportion, and then feeding the mixture into a reactor for reaction, wherein the molar ratio of the methanol to the ammonia gas to the air is 1: x: y, wherein x is 0.5-5 and y is 80-100; the reaction temperature is 300-400 ℃, the catalyst is filled by 50mL, and the total volume space velocity is 1000-3000h-1。
10. The method as claimed in claim 9, wherein the reaction material is preheated and then enters the reaction tube, and the preheating temperature is 100 ℃ and 250 ℃.
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| CN115818668A (en) * | 2022-10-27 | 2023-03-21 | 万华化学集团股份有限公司 | Method for preparing hydrocyanic acid by ammoxidation of methanol |
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