CN101961650B - Zirconium base catalyst, preparation method and application in preparation of anhydrous formaldehyde - Google Patents
Zirconium base catalyst, preparation method and application in preparation of anhydrous formaldehyde Download PDFInfo
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- CN101961650B CN101961650B CN2010102788285A CN201010278828A CN101961650B CN 101961650 B CN101961650 B CN 101961650B CN 2010102788285 A CN2010102788285 A CN 2010102788285A CN 201010278828 A CN201010278828 A CN 201010278828A CN 101961650 B CN101961650 B CN 101961650B
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Abstract
The invention belongs to the technical field of chemical industries and discloses a novel zirconium base catalyst for preparing anhydrous formaldehyde via the non-oxidative dehydrogenation of methanol. The catalyst is prepared by the steps of: mixing the zirconium and auxiliaries nitrate and silica sol with a precipitant to perform uniform precipitation by using a uniform total precipitation method under the conditions of thermostatic waterbath and high-speed mixing; and carrying out aging, filtration, washing, shaping, roasting and the like. The catalyst is applied to the reaction of preparing the anhydrous formaldehyde via the direct dehydrogenation of the methanol, can be prepared in a condition that the relative temperature is lower, and has the advantages of simple preparation method, free of precious metal, low cost, high catalytic activity, longer service life, and industrial applicability.
Description
Technical field
The invention belongs to chemical technology field, be specifically related to a kind ofly be used for the non-oxide dehydrogenation of methyl alcohol and prepare Zirconium-base catalyst of anhydrous formaldehyde and preparation method thereof.
Background technology
Formaldehyde is a kind of very important organic chemical industry's basic material; Be widely used in the intermediate of chemical products such as producing acetal resin, Lauxite, phenolic resins, pentaerythrite, methenamine and medicine and agricultural chemicals; In most of field, water content has high requirement in the PARA FORMALDEHYDE PRILLS(91,95) solution.
Contain a large amount of water in the formaldehyde of produced in conventional processes, obtain anhydrous formaldehyde, need the industrial formol product is carried out distillation operation; Because formalin relative ideal solution is the minus deviation of certain value; Cause forming azeotropic system, the dehydration separating effect is not good enough, has increased production cost greatly.And adopt the non-oxide dehydriding of methyl alcohol, can directly obtain anhydrous formaldehyde.It is a kind of new process of remarkable in economical benefits.
The special public clear 47-19251 report of existing patent is opened the metal alloy catalyst that clear 52-215 forms with copper, zinc, selenium by zinc, potassium, the alloy of pluging with molten metal and the spy of fusion, and mostly the life-span is short, reactivity is low for these catalyst, does not have industrial application value; And patent Appl.Catal.A.Gen, the catalyst containing sodium of 2001 (213) 203 reports, the formaldehyde yield brings up to 70%, but owing to problems such as its catalyst life and regeneration are restricted its industrial applications.Japanese Patent Laid is opened the Ag-SiO of clear 60-89441 report
2The selectivity of-ZnO catalyst PARA FORMALDEHYDE PRILLS(91,95) is on the low side, does not have industrial application value.Chinese patent CN200310108127.7 and CN 200310108720.1 adopt the Ag-SiO of sol-gel process (SOL-GEL method) preparation
2-MgO-Al
2O
3, Ag-SiO
2-Al
2O
3The yield of-ZnO formaldehyde can be up to 95.6%, because of problems such as its reaction temperature and catalyst life and regeneration have limited its industrial applications; The Alkali-Metal Na of CN 200710139668.4 reports
2CO
3Catalyst, formaldehyde yield 45.16%, catalytic effect remains unchanged basically in the 55h, but its reaction temperature carries out under 973K, and the suitability for industrialized production that is unrealized.
The inventor has prepared Zirconium-base catalyst and has been applied to the reaction that the non-oxide dehydrogenation of methyl alcohol prepares anhydrous formaldehyde, lays a good foundation for realizing the industrialization of producing the anhydrous formaldehyde process from methyl alcohol.The present invention provides a kind of preparation method that the non-oxide dehydrogenation of methyl alcohol prepares the industrial catalyst of anhydrous formaldehyde process that is used for.
Summary of the invention
The objective of the invention is to propose a kind of zirconium based dehydrogenation catalyst and Preparation of catalysts method.Compare with other catalyst, this catalyst has that the preparation method is easy, cost is cheap, the selectivity advantages of higher, and catalyst is less demanding to reaction temperature, production process continuously, have a reaction stability preferably.
Technical scheme of the present invention is following:
The following compositions that zirconium based dehydrogenation catalyst of the present invention contains is in mass formed, and its major catalyst comprises 1～15 part zirconia, carrier comprise 70～95 parts be selected from alundum (Al, Ludox or silica, preferred: Ludox; Catalyst further contains one or more oxides that are selected from manganese, iron, copper, silver, zinc, nickel, lanthanum, calcium, barium, magnesium of 0～10 part as co-catalyst, and is preferred: the oxide of zinc or iron.
Zirconium based dehydrogenation catalyst of the present invention is made by sluggish precipitation, and this process comprises steps such as deposition, filtration, washing, moulding, drying, roasting, and concrete preparation method is following:
(1) in 90 ℃ of waters bath with thermostatic control, precursor, Ludox and precipitating reagent with solubility zirconates, one or more co-catalysts under the high-speed stirred carry out co-precipitation; Precipitate complete continued and stir 1.5h, still aging 1h in 80 ℃ of waters bath with thermostatic control spends the night then; Again with sedimentation and filtration, washing, extruding slivering; Prepared precipitated catalyst parent is at 100～150 ℃ of down dry 5～24h; Preferably at 110～130 ℃ of down dry 8～12h; The roasting under certain atmosphere of dried catalyst, the atmosphere of roasting is air, oxygen, nitrogen or hydrogen, is preferably nitrogen; Sintering temperature is 450～750 ℃, 550～650 ℃ of preferable range; Roasting time is 15～35h, and preferred 20～24h, the sediment after the roasting be through screening 10～60 orders, and preferred 20～40 orders are subsequent use; Nitrate or chloride that wherein said solubility zirconates is a zirconium;
Wherein said co-catalyst precursor is with general formula AB
xRepresent:
A is Mn
2+, Fe
3+, Ag
+, Zn
2+, Ni
2+, La
2+, Ca
2+, Ba
2+Or Mg
2+
B is NO
3 -, Cl
-X:1～3.
Preferred A is: Zn
2+, Fe
3+B is NO
3 -
Wherein said precipitating reagent is one or more in NaOH, potash, sodium carbonate, ammonium carbonate, the urea.Preferably: urea.
Zirconium based dehydrogenation catalyst of the present invention is that the direct non-oxide dehydrogenation of raw material prepares anhydrous formaldehyde with methyl alcohol, and the catalytic dehydrogenating reaction course of being carried out is following:
The present invention is continued operation; The fixed bed quartz tube reactor on-line measuring device that is adopted in the course of reaction is packed into the catalyst that makes in the quartz reactor, uses the inert gas purge reactor; Remove air and impurity that inside retains; Feed protection gas and carry out preheating, wherein source of the gas has hydrogen, nitrogen, helium, nitrogen; Wherein the methyl alcohol volume content is 10%～60%, preferred 35%～55%; Reaction temperature is 250～800 ℃, preferred 450～650 ℃; The mass space velocity of bed is 5～85mlg
-1Cats
-1, preferred 20～55mlg
-1Cats
-1
In the catalytic dehydrogenating reaction process, through the optimization of reaction condition, reactions step is rested on as far as possible generate the formaldehyde stage, reduce the generation of by-product.With this understanding, conversion of methanol is greater than 98%, and the selectivity of formaldehyde is greater than 60%.
The present invention compared with prior art advantage is remarkable: one, the zirconium based dehydrogenation catalyst that makes of the present invention; Be applied in the reaction of the non-oxide dehydrogenation system anhydrous formaldehyde of methyl alcohol; Compare with other similar catalysts, can under the lower condition of relative temperature, carry out, yield can reach 60%.Two, this Preparation of Catalyst is simple, does not contain noble metal, and is with low cost.Three, catalytic dehydrogenation processes realizes in fixed bed reactors, and process is continuous, has significantly improved reaction efficiency, has shortened the operating time.Four, this catalyst is insensitive to response parameter, broad between the operating space, and elasticity is big, is convenient to production control, is suitable for industry and goes up application.
Description of drawings
Fig. 1 is the preparation flow figure of Zirconium-base catalyst of the present invention;
Fig. 2 prepares the reaction process flow process flow chart of anhydrous formaldehyde for catalytic dehydrogenation of the present invention;
Fig. 3 is fixed bed reactors constructional device figure used in the present invention, 1 injector wherein, 2 quartz sands, 3 catalyst, 4 heat-insulation layers, 5 heating tubes, 6 condensers, 7 electric heating lotus roots, 8 gatherers.
The specific embodiment
The present invention is continued operation, the fixed bed quartz tube reactor on-line measuring device that is adopted in the course of reaction, and its constructional device figure sees shown in the Figure of description 3.Wherein in the middle of the heating tube 5 of fixed-bed tube reactor electric heating lotus root 7 is housed, can the assaying reaction temperature, its outer one deck heat-insulation layer 4 that covers helps keeping the temperature constant state in the heating tube 5, and catalyst 3 is equipped with in the centre of heating tube, and quartz sand 2 is equipped with at two ends.The catalytic dehydrogenating reaction technological process is seen shown in the Figure of description 2.Material benzenemethanol together with carrier gas nitrogen according to a certain percentage; Vaporize greater than 100 ℃ preheater preheating through temperature through injector 1; Get into fixed bed reactors together; Methyl alcohol after the vaporization carries out dehydrogenation reaction in the fixed bed reactors of catalyst are housed, product carries out the gas-chromatography on-line analysis from passage, and another paths gets into gatherer 8 after cooler 6 coolings.
Embodiment 1
1, Preparation of catalysts and preliminary treatment: with 4.1g Zr (NO
3)
45H
2O, 0.5g Zn (NO
3)
26H
2O and 0.3gFe (NO
3)
39H
2O is dissolved in deionized water, with 100g 30% (Wt, SiO
2) mixing of acidic silicasol solution, to wherein adding 4.3g sodium carbonate, in 90 ℃ of waters bath with thermostatic control, constantly stir again, precipitate complete continued and stir 1.5h, still aging 1h in 80 ℃ of waters bath with thermostatic control spends the night then.With sedimentation and filtration, washing, extruding slivering, prepared precipitated catalyst parent is dry 5h under 100 ℃ again, the roasting under air of dried catalyst, and sintering temperature is 400 ℃, roasting 15h, the sediment after the roasting is through screening 10 orders.Promptly obtaining major catalyst is 3.7%ZrO
4, co-catalyst is 0.43%ZnO, 0.38%Fe
2O
3, carrier is 95.4%SiO
2Catalyst.
2, catalytic dehydrogenation: temperature of reactor is raised to 450 ℃., feed carrier gas nitrogen, methyl alcohol is squeezed in the fixed bed reactors through micro pump, and wherein the methyl alcohol volume content is 5%.The mass space velocity of bed is 20mlg
-1Cats
-1
3, experimental result: under this condition, conversion of methanol 96.4%, the selectivity 55% of formaldehyde.
Embodiment 2
1, Preparation of catalysts and preliminary treatment: with 6.3g Zr (NO
3)
45H
2O, 4.2g Mn (NO
3)
2With 2.7g Fe (NO
3)
39H
2O is dissolved in deionized water, with 100g 30% (Wt, SiO
2) mixing of acidic silicasol solution, to wherein adding the 14.6g ammonium carbonate, following steps are with embodiment 1 again.Prepared precipitated catalyst parent is dry 6h under 110 ℃, the roasting under nitrogen of dried catalyst, and sintering temperature is 500 ℃, roasting 18h, the sediment after the roasting is through screening 20 orders.Promptly obtaining major catalyst is 5.5%ZrO
4, co-catalyst is 2.8%MnO
2, 3.6%Fe
2O
3, carrier is 91.4%SiO
2Catalyst.
2, catalytic dehydrogenation: temperature of reactor is raised to 450 ℃., feed carrier gas nitrogen, methyl alcohol is squeezed in the fixed bed reactors through micro pump, and wherein the methyl alcohol volume content is 20%, and the mass space velocity of bed is 35mlg
-1Cats
-1
3, experimental result: under this condition, conversion of methanol 98.3%, the selectivity 57% of formaldehyde.
Embodiment 3
1, Preparation of catalysts and preliminary treatment: with 11.3g Zr (NO
3)
45H
2O, 7.1g Mg (NO
3)
22H
2O and 3.7gFe (NO
3)
39H
2O is dissolved in deionized water, with 100g 30% (Wt, SiO
2) mixing of acidic silicasol solution, to wherein adding 18.6g NaOH, following steps are with embodiment 1 again.Prepared precipitated catalyst parent is dry 8h under 120 ℃, the roasting under nitrogen of dried catalyst, and sintering temperature is 550 ℃, roasting 20h, the sediment after the roasting is through screening 30 orders.Promptly obtaining major catalyst is 9.9%ZrO
4, co-catalyst is 4.3%MnO
2, 4.0%Fe
2O
3, carrier is 82.7%SiO
2Catalyst.
2, catalytic dehydrogenation: temperature of reactor is raised to 500 ℃., feed carrier gas nitrogen, methyl alcohol is squeezed in the fixed bed reactors through micro pump, and wherein the methyl alcohol volume content is 40%, and the mass space velocity of bed is 30mlg
-1Cats
-1
3, experimental result: under this condition, conversion of methanol 99.5%, the selectivity 62% of formaldehyde.
Embodiment 4
1, Preparation of catalysts and preliminary treatment: with 11.3g Zr (NO
3)
45H
2O, 5.2g Zn (NO
3)
26H
2O is dissolved in deionized water, with 100g 30% (Wt, SiO
2) mixing of acidic silicasol solution, to wherein adding 16.3g urea, following steps are with embodiment 1 again.Prepared precipitated catalyst parent is dry 10h under 125 ℃, the roasting under air of dried catalyst, and sintering temperature is 550 ℃, and roasting 22h, the sediment after the roasting are through screening 30 orders, and promptly obtaining major catalyst is 9.4%ZrO
4, co-catalyst is that 4.1%ZnO, carrier are 86.5%SiO
2Catalyst.
2, catalytic dehydrogenation: temperature of reactor is raised to 550 ℃., feed carrier gas nitrogen, methyl alcohol is squeezed in the fixed bed reactors through micro pump, and wherein the methyl alcohol volume content is 35%, and the mass space velocity of bed is 35mlg
-1Cats
-1
3, experimental result: under this condition, conversion of methanol 98.3%, the selectivity 60.4% of formaldehyde.
Embodiment 5
1, Preparation of catalysts and preliminary treatment: with 8.8g Zr (NO
3)
45H
2O, 1.9g ZnCl
2With 1.8g Fe (NO
3)
39H
2O is dissolved in deionized water, with 100g 30% (Wt, SiO
2) mixing of acidic silicasol solution, to wherein adding 10.4g urea, following steps are with embodiment 1 again.Prepared precipitated catalyst parent is dry 12h under 140 ℃, the roasting under air of dried catalyst, and sintering temperature is 650 ℃, roasting 24h, the sediment after the roasting is through screening 40 orders.Promptly obtaining major catalyst is 7.4%ZrO
4, co-catalyst is 3.3%ZnO, 2.0%Fe
2O
3, carrier is 86.5%SiO
2Catalyst.
2, catalytic dehydrogenation: temperature of reactor is raised to 600 ℃., feed carrier gas nitrogen, methyl alcohol is squeezed in the fixed bed reactors through micro pump, and wherein the methyl alcohol volume content is 50%, and the mass space velocity of bed is 55mlg
-1Cats
-1
3, experimental result: under this condition, conversion of methanol 97.4%, the selectivity 58.4% of formaldehyde.
Embodiment 6
1, Preparation of catalysts and preliminary treatment: with 12.8g Zr (NO
3)
45H
2O, 5.9g Ca (NO
3)
2With 1.2g Fe (NO
3)
39H
2O is dissolved in deionized water, with 100g 30% (Wt, SiO
2) mixing of acidic silicasol solution, to wherein adding 18.9g sodium carbonate, following steps are with embodiment 1 again.Prepared precipitated catalyst parent is dry 24h under 150 ℃, the roasting under air of dried catalyst, and sintering temperature is 750 ℃, roasting 35h, the sediment after the roasting is through screening 60 orders.Promptly obtaining major catalyst is 9.8%ZrO
4, co-catalyst is 8.7%CaO, 1.3%Fe
2O
3, carrier is 80.3%SiO
2Catalyst.
2, catalytic dehydrogenation: temperature of reactor is raised to 800 ℃., feed carrier gas nitrogen, methyl alcohol is squeezed in the fixed bed reactors through micro pump, and wherein the methyl alcohol volume content is 55%.The mass space velocity of bed is 85mlg
-1Cats
-1
3, experimental result: under this condition, conversion of methanol 95.7%, the selectivity 55.4% of formaldehyde.
Claims (2)
1. the preparation method of zirconium based dehydrogenation catalyst, its following compositions that contains is in mass formed, and its major catalyst comprises 1～15 part zirconia, and carrier comprises 70～95 parts Ludox; Catalyst further contains 0～10 part one or more zinc or the oxide of iron, it is characterized in that concrete preparation method is following:
(1) in 90 ℃ of waters bath with thermostatic control, precursor, Ludox and precipitating reagent with solubility zirconates, one or more co-catalysts under the high-speed stirred carry out co-precipitation; Precipitate complete continued and stir 1.5h, still aging 1h in 80 ℃ of waters bath with thermostatic control spends the night then; With sedimentation and filtration, washing, extruding slivering, prepared precipitated catalyst parent is dry 5～24h under 100～150 ℃ again, the roasting under certain atmosphere of dried catalyst, and the atmosphere of roasting is air, oxygen, nitrogen or hydrogen; Sintering temperature is 450～750 ℃; Roasting time is 15～35h, and the sediment after the roasting is through screening 10～60 orders, and is subsequent use; Nitrate or chloride that wherein said solubility zirconates is a zirconium;
Wherein said co-catalyst precursor is with general formula AB
xRepresent:
A is Fe
3+Or Zn
2+
B is NO
3 -, Cl
-X:1～3;
Wherein said precipitating reagent is one or more in NaOH, potash, sodium carbonate, ammonium carbonate, the urea.
2. the preparation method of zirconium based dehydrogenation catalyst according to claim 1; It is characterized in that concrete preparation method is following: (1) prepared precipitated catalyst parent is at 110～130 ℃ of down dry 8～12h; The roasting under certain atmosphere of dried catalyst, the atmosphere of roasting are nitrogen; Sintering temperature is 550～650 ℃; Roasting time is 15～35h, and the sediment after the roasting is subsequent use through screening 20～40 orders; Wherein said co-catalyst precursor is represented with general formula ABx: wherein A is: Zn
2+, Fe
3+B is NO
3 -Wherein said precipitating reagent is a urea.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105712857A (en) * | 2014-12-03 | 2016-06-29 | 中国科学院大连化学物理研究所 | Method for preparing anhydrous formaldehyde by dehydrogenation of absolute methanol |
| CN106925259A (en) * | 2015-12-31 | 2017-07-07 | 中国石油天然气股份有限公司 | FCC Off-Gas over Zeolite Catalyst propylene hydration prepares catalyst of isopropanol and its preparation method and application |
| CN111097461A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Catalyst for preparing formaldehyde by methanol oxidation |
| CN112191264B (en) * | 2020-10-28 | 2022-02-18 | 安徽大学 | Manganese dioxide composite material and preparation method and application thereof |
Citations (4)
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|---|---|---|---|---|
| CN1390639A (en) * | 2002-06-13 | 2003-01-15 | 复旦大学 | Carried siver catalyst for preparing anhydrous formaldehyde and its preparing process |
| US20040038811A1 (en) * | 2000-11-03 | 2004-02-26 | Adolfo Parmaliana | Fe-doped silica catalyst |
| CN101147872A (en) * | 2007-10-27 | 2008-03-26 | 太原理工大学 | Method for preparing anhydrous formaldehyde industrial catalyst by methanol dehydrogenation |
| US7491852B1 (en) * | 2007-12-07 | 2009-02-17 | National Tsing Hua University | Process for preparing aldehyde or ketone by oxidation of alcohol with a catalyst having a core-porous shell structure |
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2010
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040038811A1 (en) * | 2000-11-03 | 2004-02-26 | Adolfo Parmaliana | Fe-doped silica catalyst |
| CN1390639A (en) * | 2002-06-13 | 2003-01-15 | 复旦大学 | Carried siver catalyst for preparing anhydrous formaldehyde and its preparing process |
| CN101147872A (en) * | 2007-10-27 | 2008-03-26 | 太原理工大学 | Method for preparing anhydrous formaldehyde industrial catalyst by methanol dehydrogenation |
| US7491852B1 (en) * | 2007-12-07 | 2009-02-17 | National Tsing Hua University | Process for preparing aldehyde or ketone by oxidation of alcohol with a catalyst having a core-porous shell structure |
Non-Patent Citations (1)
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| 张藩贤等.负载型氧化锆催化剂上甲醇脱氢制甲醛.《催化学报》.1993,第14卷(第2期),第139页-第142页. * |
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Effective date of registration: 20151021 Address after: Tai Zhen Du tou street 213311 Jiangsu province Changzhou City 8-2 No. 7 Patentee after: Liyang Chang Technology Transfer Center Co., Ltd. Address before: Gehu Lake Road Wujin District 213164 Jiangsu city of Changzhou province No. 1 Patentee before: Changzhou University |