CN107262105A - 一种甲醇生产甲醛用的催化剂及其制备方法 - Google Patents
一种甲醇生产甲醛用的催化剂及其制备方法 Download PDFInfo
- Publication number
- CN107262105A CN107262105A CN201710554293.1A CN201710554293A CN107262105A CN 107262105 A CN107262105 A CN 107262105A CN 201710554293 A CN201710554293 A CN 201710554293A CN 107262105 A CN107262105 A CN 107262105A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- methanol production
- parts
- preparation
- formaldehyde
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 90
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 239000003054 catalyst Substances 0.000 title claims abstract description 46
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000011148 porous material Substances 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 14
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical class [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011230 binding agent Substances 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- 150000002751 molybdenum Chemical class 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 8
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 5
- 150000003863 ammonium salts Chemical class 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000007493 shaping process Methods 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 3
- 239000012188 paraffin wax Substances 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000012752 auxiliary agent Substances 0.000 claims description 2
- 230000033228 biological regulation Effects 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 239000007767 bonding agent Substances 0.000 claims 1
- DSMZRNNAYQIMOM-UHFFFAOYSA-N iron molybdenum Chemical compound [Fe].[Fe].[Mo] DSMZRNNAYQIMOM-UHFFFAOYSA-N 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 7
- 238000006356 dehydrogenation reaction Methods 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 21
- 239000000047 product Substances 0.000 description 11
- KWUUWVQMAVOYKS-UHFFFAOYSA-N iron molybdenum Chemical compound [Fe].[Fe][Mo][Mo] KWUUWVQMAVOYKS-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 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
- 238000003786 synthesis reaction Methods 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 2
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical group [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229960004011 methenamine Drugs 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 241000254173 Coleoptera Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- ITFCTBFBEKRKDC-UHFFFAOYSA-N [O].OC Chemical compound [O].OC ITFCTBFBEKRKDC-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- -1 alkali metal salt Chemical class 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/881—Molybdenum and iron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8876—Arsenic, antimony or bismuth
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8898—Manganese, technetium or rhenium containing also molybdenum
-
- 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
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
- C07C45/38—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups being a primary hydroxyl group
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
本发明属于化工技术领域，特别是涉及一种甲醇生产甲醛用的催化剂及其制备方法，以重量份计，由可溶性铁盐3～8份、可溶性钼盐9～14份、辅助造孔剂0.03～0.1份、助剂金属0.2～0.8份以及粘结剂0.1～0.6份。本发明制备的催化剂表面积高，孔径和孔容大，使得该催化剂具有较好的低温催化脱氢活性，深度脱氢能力及稳定性，有利于传质传热，提高甲醇的转化率和甲醛的收率。
Description
技术领域
本发明涉及化工技术领域，具体来说，涉及一种甲醇生产甲醛用的催化剂及其制备方法。
背景技术
甲醛是脂肪族系列中最简单的醛，化学性质十分活泼，可合成多种化合物。它是重要的基本化工原料之一，广泛应用于化工、医药、染料和农业等领域。大部分用作脲醛树脂、酚醛树脂和氨基树脂的原料，其次用于生产聚甲醛、三羟甲基丙烷、季戊四醇、乌洛托品、吡啶和异戊二烯等化工产品，甲醛还可用作合成香料、合成炸药、合成螯合剂、合成助剂以及合成重要的中间体等。
工业生产甲醛多采用甲醇氧化法。按理论计算，其产品为甲醛和水的混合物(摩尔比例1:1)。由于甲醛水溶液的蒸汽压较低且甲醛和水形成共沸物，分离和提纯制备无水甲醛能耗高。但是，合成树脂和制备乌洛托品等生产过程，需要无水甲醛，其需求量逐渐增加。甲醇无氧脱氢工艺得到的甲醛和副产物氢气很容易分离，且无水生成，避免了甲醛水溶液的分离操作，而且副产物为氢气，可循环用于合成甲醇；同时，该反应不会出现甲醇氧化生成甲酸腐蚀设备的问题，从而有利于甲醛溶液的稳定和净化。近年来，研究甲醇无氧条件下制备甲醛的重点主要在新催化剂的开发，包括金属及其氧化物催化剂、碱金属盐和分子筛催化剂等几类。虽然现有的催化剂都能催化甲醇生成甲醛，但都存在催化剂的焙烧温度较高、催化剂强度较低、使用寿命低、甲醇转化率低、催化反应温度较高等问题。
发明内容
有鉴于此，本发明的目的是提供一种甲醇生产甲醛用的催化剂，以解决现有催化剂反应温度较高、甲醇转化率低的技术问题。
本发明通过以下技术方案解决上述技术问题：
一种甲醇生产甲醛用的催化剂，以重量份计，由可溶性铁盐3～8份、可溶性钼盐9～14份、辅助造孔剂0.03～0.1份、助剂金属0.2～0.8份以及粘结剂0.1～0.6份组成。
优选的，由可溶性铁盐4～7份、可溶性钼盐10～13份、辅助造孔剂0.05～0.08份、助剂金属0.3～0.7份以及粘结剂0.2～0.5份组成。
更优选的，由可溶性铁盐5份、可溶性钼盐12份、辅助造孔剂0.06份、助剂金属0.5份以及粘结剂0.3份组成。
所述甲醇生产甲醛用的催化剂的制备方法，包括以下步骤：
(1)将可溶性铵盐加入到装有去离子水的沉淀桶中，配成质量浓度为10～30％的水溶液；
(2)将步骤(1)中的沉淀桶升温至40～80℃，然后按比例加入可溶性铁盐及助剂金属，配成质量浓度为8～20％的溶液，调节溶液pH值为1～3，保持恒温搅拌反应0.5～2h；
(3)向步骤(2)中获得的溶液中按比例添加辅助造孔剂，搅拌至溶解；
(4)将步骤(3)所得的溶液放入坩埚中，在60～100℃的恒温水浴中老化处理3～6h；
(5)将步骤(4)老化处理后的溶液先进行洗涤，接着干燥至产物的水分含量为5～12％；
(6)将干燥处理后的产物与粘结剂混合均匀，接着将该混合物进行焙烧，焙烧的温度为450～600℃，时间为3～6h，焙烧后经成型即制得铁模法催化剂。
所述的辅助造孔剂为脂、石腊、有机低聚物、树脂或聚醚中的任何一种或任何两种的混合物。
所述步骤(2)中，采用硝酸铵调节溶液的pH值。
所述铁钼法催化剂为球状、圆柱状、环状或粉状。
所述助剂金属为铝、铋或锰中的任意一种。
所述的粘结剂为金属硅或钛。
所述干燥的温度为100～120℃。
所述可溶性钼盐为七钼酸、四钼酸或二钼酸。
所述可溶性铁盐为氯化铁、硝酸铁或醋酸铁。
本发明的有益效果在于：本发明制备的催化剂表面积高，孔径和孔容大，其比表面积为250～321m2/g，孔容为0.308～0.525ml/g，使得该催化剂具有较好的低温催化脱氢活性，深度脱氢能力及稳定性，有利于传质传热，提高甲醇的转化率和甲醛的收率。
具体实施方式
为了方便本领域的技术人员理解，下面将结合实施例对本发明做进一步的描述。实施例仅仅是对该发明的举例说明，不是对本发明的限定，实施例中未作具体说明的步骤均是已有技术，在此不做详细描述。
实施例一
原料：
氯化铁3kg、七钼酸9kg、脂0.03kg、铝0.2kg以及硅0.1kg。
制备方法：
(1)将可溶性铵盐加入到装有去离子水的沉淀桶中，配成质量浓度为10％的水溶液；
(2)将步骤(1)中的沉淀桶升温至40℃，然后按比例加入可溶性铁盐及助剂金属，配成质量浓度为8％的溶液，采用硝酸铵调节溶液pH值为1，保持恒温搅拌反应0.5h；
(3)向步骤(2)中获得的溶液中按比例添加辅助造孔剂，搅拌至溶解；
(4)将步骤(3)所得的溶液放入坩埚中，在60℃的恒温水浴中老化处理3h；
(5)将步骤(4)老化处理后的溶液先进行洗涤，接着干燥，干燥温度为100℃，干燥至产物的水分含量为5％；
(6)将干燥处理后的产物与粘结剂混合均匀，接着将该混合物进行焙烧，焙烧的温度为450℃，时间为3h，焙烧后经成型即制得铁模法催化剂。经测定，该催化剂的比表面积为250m2/g，孔容为0.308ml/g。
所述铁钼法催化剂为球状、圆柱状、环状或粉状。
实施例二
原料：
醋酸铁8kg、二钼酸14kg、石腊0.1kg、铋0.8kg以及钛0.6kg。
制备方法：
(1)将可溶性铵盐加入到装有去离子水的沉淀桶中，配成质量浓度为30％的水溶液；
(2)将步骤(1)中的沉淀桶升温至80℃，然后按比例加入可溶性铁盐及助剂金属，配成质量浓度为20％的溶液，采用硝酸铵调节溶液pH值为3，保持恒温搅拌反应2h；
(3)向步骤(2)中获得的溶液中按比例添加辅助造孔剂，搅拌至溶解；
(4)将步骤(3)所得的溶液放入坩埚中，在100℃的恒温水浴中老化处理6h；
(5)将步骤(4)老化处理后的溶液先进行洗涤，接着干燥，干燥温度为120℃，干燥至产物的水分含量为12％；
(6)将干燥处理后的产物与粘结剂混合均匀，接着将该混合物进行焙烧，焙烧的温度为600℃，时间为6h，焙烧后经成型即制得铁模法催化剂。经测定，该催化剂的比表面积为264m2/g，孔容为0.396ml/g。
所述铁钼法催化剂为球状、圆柱状、环状或粉状。
实施例三
原料：
硝酸铁5kg、四钼酸12kg、树脂0.06kg、锰0.5kg以及硅0.3kg。
制备方法：
(1)将可溶性铵盐加入到装有去离子水的沉淀桶中，配成质量浓度为20％的水溶液；
(2)将步骤(1)中的沉淀桶升温至60℃，然后按比例加入可溶性铁盐及助剂金属，配成质量浓度为14％的溶液，采用硝酸铵调节溶液pH值为2，保持恒温搅拌反应0.9h；
(3)向步骤(2)中获得的溶液中按比例添加辅助造孔剂，搅拌至溶解；
(4)将步骤(3)所得的溶液放入坩埚中，在80℃的恒温水浴中老化处理5h；
(5)将步骤(4)老化处理后的溶液先进行洗涤，接着干燥，干燥温度为110℃，干燥至产物的水分含量为8％；
(6)将干燥处理后的产物与粘结剂混合均匀，接着将该混合物进行焙烧，焙烧的温度为500℃，时间为4h，焙烧后经成型即制得铁模法催化剂。经测定，该催化剂的比表面积为321m2/g，孔容为0.525ml/g。
所述铁钼法催化剂为球状、圆柱状、环状或粉状。
试验例
甲醇氧化制甲醛反应评价在管式固定床反应器中进行，将3ml催化剂填充在反应器中，使用15％氧气/氮气作为氧化气，常压下，流速未73L/h，甲醇进量9ml/h，反应温度为240℃。气相色谱定量分析，计算甲醇的转化率和甲醛的收率。结果如表1：
表1
| 催化剂 | 甲醇转化率(％) | 甲醛收率(％) |
| 实施例一 | 99.1 | 92.0 |
| 实施例二 | 99.3 | 92.7 |
| 实施例三 | 99.8 | 93.3 |
| 现有催化剂 | 85.3 | 81.9 |
从表1中可以看出，与现有的铁钼法催化剂相比，本发明制备的催化剂，无论是甲醇的转化率还是甲醛的收率，均明显高于现有的铁钼法催化剂。并且本发明的催化剂催化反应温度较低，有利于降低生产成本。
Claims (10)
1.一种甲醇生产甲醛用的催化剂，其特征在于：以重量份计，由可溶性铁盐3～8份、可溶性钼盐9～14份、辅助造孔剂0.03～0.1份、助剂金属0.2～0.8份以及粘结剂0.1～0.6份组成。
2.如权利要求1所述的甲醇生产甲醛用的催化剂，其特征在于：由可溶性铁盐4～7份、可溶性钼盐10～13份、辅助造孔剂0.05～0.08份、助剂金属0.3～0.7份以及粘结剂0.2～0.5份组成。
3.如权利要求1所述的甲醇生产甲醛用的催化剂，其特征在于：由可溶性铁盐5份、可溶性钼盐12份、辅助造孔剂0.06份、助剂金属0.5份以及粘结剂0.3份组成。
4.如权利要求1～3任意一项所述的甲醇生产甲醛用的催化剂的制备方法，其特征在于：包括以下步骤：
(1)将可溶性铵盐加入到装有去离子水的沉淀桶中，配成质量浓度为10～30％的水溶液；
(2)将步骤(1)中的沉淀桶升温至40～80℃，然后按比例加入可溶性铁盐及助剂金属，配成质量浓度为8～20％的溶液，调节溶液pH值为1～3，保持恒温搅拌反应0.5～2h；
(3)向步骤(2)中获得的溶液中按比例添加辅助造孔剂，搅拌至溶解；
(4)将步骤(3)所得的溶液放入坩埚中，在60～100℃的恒温水浴中老化处理3～6h；
(5)将步骤(4)老化处理后的溶液先进行洗涤，接着干燥至产物的水分含量为5～12％；
(6)将干燥处理后的产物与粘结剂混合均匀，接着将该混合物进行焙烧，焙烧的温度为450～600℃，时间为3～6h，焙烧后经成型即制得铁模法催化剂。
5.如权利要求4所述的甲醇生产甲醛用的催化剂的制备方法，其特征在于：所述的辅助造孔剂为脂、石腊、有机低聚物、树脂或聚醚中的任何一种或任何两种的混合物。
6.如权利要求4所述的甲醇生产甲醛用的催化剂的制备方法，其特征在于：所述步骤(2)中，采用硝酸铵调节溶液的pH值。
7.如权利要求4所述的甲醇生产甲醛用的催化剂的制备方法，其特征在于：所述铁钼法催化剂为球状、圆柱状、环状或粉状。
8.如权利要求4所述的甲醇生产甲醛用的催化剂的制备方法，其特征在于：所述助剂金属为铝、铋或锰中的任意一种。
9.如权利要求4所述的甲醇生产甲醛用的催化剂的制备方法，其特征在于：所述的粘结剂为金属硅或钛。
10.如权利要求4所述的甲醇生产甲醛用的催化剂的制备方法，其特征在于：所述干燥的温度为100～120℃。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710554293.1A CN107262105A (zh) | 2017-07-10 | 2017-07-10 | 一种甲醇生产甲醛用的催化剂及其制备方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710554293.1A CN107262105A (zh) | 2017-07-10 | 2017-07-10 | 一种甲醇生产甲醛用的催化剂及其制备方法 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107262105A true CN107262105A (zh) | 2017-10-20 |
Family
ID=60073131
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710554293.1A Pending CN107262105A (zh) | 2017-07-10 | 2017-07-10 | 一种甲醇生产甲醛用的催化剂及其制备方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107262105A (zh) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109012682A (zh) * | 2018-07-27 | 2018-12-18 | 新疆大学 | 一种甲醇氧化制甲醛铁钼催化剂的改性方法 |
| CN111229242A (zh) * | 2018-11-29 | 2020-06-05 | 中国科学院大连化学物理研究所 | 一种铈掺杂甲醇氧化制甲醛铁钼基催化剂及制备和应用 |
| CN116351463A (zh) * | 2021-12-28 | 2023-06-30 | 中国石油天然气股份有限公司 | 用于甲醇脱氢制备无水甲醛的催化剂及其制备方法和应用 |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1546232A (zh) * | 2003-12-09 | 2004-11-17 | 南化集团研究院 | 甲醇氧化制甲醛铁钼催化剂及其制备方法 |
| CN1978052A (zh) * | 2005-12-07 | 2007-06-13 | 南化集团研究院 | 甲缩醛氧化制浓甲醛铁钼催化剂及制备方法 |
| CN105457648A (zh) * | 2014-09-09 | 2016-04-06 | 中国石油化工股份有限公司 | 铁钼法甲醛合成催化剂及其制备方法 |
| CN106423182A (zh) * | 2016-09-12 | 2017-02-22 | 中南大学 | 一种铁钼复合掺杂氧化物的制备方法 |
| CN106693981A (zh) * | 2016-12-22 | 2017-05-24 | 中国科学院山西煤炭化学研究所 | 一种甲醇氧化合成甲醛的铁钼催化剂及制法和应用 |
-
2017
- 2017-07-10 CN CN201710554293.1A patent/CN107262105A/zh active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1546232A (zh) * | 2003-12-09 | 2004-11-17 | 南化集团研究院 | 甲醇氧化制甲醛铁钼催化剂及其制备方法 |
| CN1978052A (zh) * | 2005-12-07 | 2007-06-13 | 南化集团研究院 | 甲缩醛氧化制浓甲醛铁钼催化剂及制备方法 |
| CN105457648A (zh) * | 2014-09-09 | 2016-04-06 | 中国石油化工股份有限公司 | 铁钼法甲醛合成催化剂及其制备方法 |
| CN106423182A (zh) * | 2016-09-12 | 2017-02-22 | 中南大学 | 一种铁钼复合掺杂氧化物的制备方法 |
| CN106693981A (zh) * | 2016-12-22 | 2017-05-24 | 中国科学院山西煤炭化学研究所 | 一种甲醇氧化合成甲醛的铁钼催化剂及制法和应用 |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109012682A (zh) * | 2018-07-27 | 2018-12-18 | 新疆大学 | 一种甲醇氧化制甲醛铁钼催化剂的改性方法 |
| CN111229242A (zh) * | 2018-11-29 | 2020-06-05 | 中国科学院大连化学物理研究所 | 一种铈掺杂甲醇氧化制甲醛铁钼基催化剂及制备和应用 |
| CN111229242B (zh) * | 2018-11-29 | 2022-12-30 | 中国科学院大连化学物理研究所 | 一种铈掺杂甲醇氧化制甲醛铁钼基催化剂及制备和应用 |
| CN116351463A (zh) * | 2021-12-28 | 2023-06-30 | 中国石油天然气股份有限公司 | 用于甲醇脱氢制备无水甲醛的催化剂及其制备方法和应用 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102019177B (zh) | 一种羟醛缩合反应固体碱催化剂及应用 | |
| CN103586067B (zh) | 一种甲醛水溶液和乙酸合成丙烯酸的方法 | |
| KR101731650B1 (ko) | 메타크릴산 제조용 촉매의 제조 방법 및 메타크릴산의 제조 방법 | |
| CN109574799B (zh) | 一种利用异丁烯和甲醇制备3-甲基-3-丁烯-1-醇的方法 | |
| CN107262105A (zh) | 一种甲醇生产甲醛用的催化剂及其制备方法 | |
| CN102371157A (zh) | 甲基丙烯醛和甲基丙烯酸制造用催化剂及其制造方法 | |
| CN107721821B (zh) | 一种制备1,3-丙二醇的方法 | |
| CN111229265B (zh) | 一种金属改性羟基磷灰石催化剂及其制备和应用 | |
| CN107282056B (zh) | 丙烯氧化合成丙烯醛和丙烯酸的催化剂 | |
| CN112194577A (zh) | 一种糠醛及其衍生物水相加氢重排制备环戊酮类化合物的方法 | |
| JPS5924140B2 (ja) | メタクリル酸の製造法及び触媒 | |
| CN111229266B (zh) | 一种负载型羟基磷灰石催化剂及其制备和应用 | |
| CN109731592A (zh) | 甲基丙烯醛选择性氧化制甲基丙烯酸的催化剂及其制备方法和用途 | |
| CN107282054B (zh) | 合成丙烯醛和丙烯酸的催化剂 | |
| CN107282057B (zh) | 用于合成丙烯醛和丙烯酸的催化剂 | |
| JP2008229515A (ja) | メタクリル酸製造用触媒の製造方法 | |
| CN103120941B (zh) | 不含氧化钾的脱氢催化剂 | |
| CN107233885B (zh) | 一种用于空气氧化催化剂的制备方法 | |
| CN107445828B (zh) | 合成乙醛酸酯的方法 | |
| KR101629003B1 (ko) | 글리세린 탈수반응용 촉매, 이의 제조 방법 및 아크롤레인의 제조 방법 | |
| CN106881123B (zh) | 复合氧化物催化剂及其制备方法和用途 | |
| EP2952498A1 (en) | Dehydration of 2,3-butanediole | |
| JPS5927217B2 (ja) | メタクリル酸製造用触媒の製法 | |
| CN109248699A (zh) | 环己烷氧化制ka油的方法 | |
| CN113999093B (zh) | 一种制备缩醛的方法 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20171020 |
|
| RJ01 | Rejection of invention patent application after publication |