CN101462081A - Method for preparing catalyst for synthesizing dimethyl oxalate - Google Patents
Method for preparing catalyst for synthesizing dimethyl oxalate Download PDFInfo
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- CN101462081A CN101462081A CNA2008101766737A CN200810176673A CN101462081A CN 101462081 A CN101462081 A CN 101462081A CN A2008101766737 A CNA2008101766737 A CN A2008101766737A CN 200810176673 A CN200810176673 A CN 200810176673A CN 101462081 A CN101462081 A CN 101462081A
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- CN
- China
- Prior art keywords
- catalyst
- reaction
- dimethyl oxalate
- metallic element
- gas
- 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.)
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- 239000003054 catalyst Substances 0.000 title claims abstract description 29
- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 11
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- BLLFVUPNHCTMSV-UHFFFAOYSA-N methyl nitrite Chemical compound CON=O BLLFVUPNHCTMSV-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract 9
- 229910002651 NO3 Inorganic materials 0.000 claims abstract 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 239000010955 niobium Substances 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- 238000002803 maceration Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
- 238000007654 immersion Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 229910000484 niobium oxide Inorganic materials 0.000 claims description 3
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 229910001868 water Inorganic materials 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 2
- 239000002184 metal Substances 0.000 claims 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims 1
- 239000012752 auxiliary agent Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 claims 1
- 238000009833 condensation Methods 0.000 claims 1
- 230000005494 condensation Effects 0.000 claims 1
- 239000011521 glass Substances 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- 239000003595 mist Substances 0.000 claims 1
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- 229910052763 palladium Inorganic materials 0.000 claims 1
- 239000008188 pellet Substances 0.000 claims 1
- 229910052709 silver Inorganic materials 0.000 claims 1
- 239000004332 silver Substances 0.000 claims 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract 2
- 229910002091 carbon monoxide Inorganic materials 0.000 abstract 2
- 238000002791 soaking Methods 0.000 abstract 2
- 238000005859 coupling reaction Methods 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- 230000000737 periodic effect Effects 0.000 abstract 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 abstract 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 14
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- YIKSCQDJHCMVMK-UHFFFAOYSA-N Oxamide Chemical class NC(=O)C(N)=O YIKSCQDJHCMVMK-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000005691 oxidative coupling reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Classifications
-
- 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
- Y02P20/141—Feedstock
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for preparing a catalyst. The catalyst can be used in the process of generation of dimethyl oxalate through oxidation coupling reaction between carbon monoxide and methyl nitrite. The catalyst is prepared by using at least one nitrate selected from metallic elements of a VIII group, an IB group and a VB group in a periodic table of elements, and soaking a carrier gamma-Al2O3 into a soaking solution. The catalyst has high conversion rate and selectivity when applied to reaction for synthesizing the carbon monoxide into the dimethyl oxalate.
Description
Technical field
The present invention relates to the preparation method of synthesizing dimethyl oxalate catalyst system therefor.Specifically, be the process that is applied to CO and methyl nitrite gas-phase dimethyloxalate synthesis.
Background technology
Dimethyl oxalate can be used for making the intermediate of oxalic acid, oxamides, ethylene glycol and some drugs and dyestuff, is a kind of important basic organic material.After nineteen sixties, discovery can utilize dimethyl oxalate synthetic important chemical material ethylene glycol after hydrogenation reaction; The alternative petroleum resources that reduce day by day of this technology are produced ethylene glycol, have important strategic and economic implications.Be that the source produces ethylene glycol in recent years with the synthesis gas, become the focus of carbon one chemical industry; This route utilizes the CO process oxidative coupling reaction elder generation synthetic mesophase product dimethyl oxalate in the synthesis gas, and dimethyl oxalate is the catalytic hydrogenation synthesizing glycol again.What the present invention narrated is the inventive method that is used for the used catalyst of synthetic intermediate dimethyl oxalate.
Summary of the invention
The object of the present invention is to provide a kind of method for preparing catalyst that is applied to synthesizing dimethyl oxalate, method provided by the invention comprises: silver nitrate, palladium nitrate, niobium oxide are dissolved in are made into maceration extract in the aqueous solution of nitric acid, then the inert carrier Al with loose structure
2O
3Soaked 1～10 hour, and after fully absorbing, isolated the immersion solid, again solid is carried out drying, 300～600 ℃ through roasting in 3～8 hours, just can be made into catalyst.CO and methyl nitrite (CH3ONO) gas phase catalysis synthesizing dimethyl oxalate ((COOCH
3)
2), reaction equation is:
The specific embodiment
Following example will illustrate further the present invention, but be not limited only to present embodiment.
Silver nitrate, palladium nitrate, niobium oxide and nitric acid and water are made into the aqueous solution, are specific area 100～300m
2The Al of/g
2O
3(diameter 4mm, long 5mm) puts into the maceration extract that has prepared, and stirs two hours, isolates the immersion solid after fully absorbing, and again solid carried out drying, 300～600 ℃ through roasting in 3～8 hours, just can be made into catalyst.
The activity of such catalysts evaluation is carried out in fixed bed stainless steel pressurized reactor, the long 500mm of reactor, Φ 15mm * 2.5mm.Reaction pressure is controlled by front and back pressure maintaining valve and counterbalance valve, pressure oscillation scope soil 0.05MPa, and temperature fluctuation range is at native 0.5K.10mL40～60 purpose the catalyst of packing in the reactor, the bed 5mL20～40 purpose inertia quartz sands of respectively packing into up and down prevent to manage interior gas channel., after the pressure maintaining valve decompression, by mass flowmenter control and measure its flow, enter reactor and react from the unstripped gas of mixed material gas cylinder.Product is collected after cooling off and is analyzed.
Through evidence, this catalyst is being used for the process of synthesizing dimethyl oxalate, has very high reactivity, and reactivity worth is stable, can carry out the running of long period.
Embodiment 1
Get Ag (NO
3)
25 grams, Pd (NO
3)
21 gram, Nb
2O
52 grams and 60% nitric acid, 10 grams are dissolved in 500 ml waters, with Al
2O
3(diameter 3mm, long 4mm, specific surface 200m
2/ g) immerse in the solution of being joined, soaked 10 hours, after fully absorbing, isolate Al
2O
3, under 120 ℃,, make catalyst through 500 ℃ of roastings after 5 hours again through oven dry in three hours.This catalyst being smashed to pieces get 10ml20～40 purpose particles after sieving, it is filled in the fixed bed reactors, is 110 ℃ in reaction temperature, volume space velocity 2000h when pressure 0.2Mpa, feeding gas then
-1Condition under react the reaction result that obtains: the methyl nitrite conversion ratio is 92.61%, dimethyl oxalate selectivity 92.42%, dimethyl oxalate yield 85.59%.
Embodiment 2
Get Ag (NO
3)
23 grams, Pd (NO
3)
21 gram, Nb
2O
51 gram and 60% nitric acid, 10 grams are dissolved in 500 ml waters, with Al
2O
3(diameter 3mm, long 4mm, specific surface 200m
2/ g) immerse in the solution of being joined, soaked 10 hours, after fully absorbing, isolate Al
2O
3, under 120 ℃,, make catalyst through 500 ℃ of roastings after 5 hours again through oven dry in three hours.This catalyst being smashed to pieces get 10ml20～40 purpose particles after sieving, it is filled in the fixed bed reactors, is 110 ℃ in reaction temperature, volume space velocity 2000h when pressure 0.2Mpa, feeding gas then
-1Condition under react the reaction result that obtains: the methyl nitrite conversion ratio is 91.30%, dimethyl oxalate selectivity 90.26%, dimethyl oxalate yield 82.41%.
Embodiment 3
Get Ag (NO
3)
25 grams, Pd (NO
3)
20.5 gram, Nb
2O
52 grams and 60% nitric acid, 10 grams are dissolved in 500 ml waters, with Al
2O
3(diameter 3mm, long 4mm, specific surface 200m
2/ g) immerse in the solution of being joined, soaked 10 hours, after fully absorbing, isolate Al
2O
3, under 120 ℃,, make catalyst through 500 ℃ of roastings after 5 hours again through oven dry in three hours.This catalyst being smashed to pieces get 10ml20～40 purpose particles after sieving, it is filled in the fixed bed reactors, is 110 ℃ in reaction temperature, volume space velocity 2000h when pressure 0.2Mpa, feeding gas then
-1Condition under react the reaction result that obtains: the methyl nitrite conversion ratio is 87.35%, dimethyl oxalate selectivity 92.16%, dimethyl oxalate yield 80.50%.
Claims (8)
1, a kind of method for preparing catalyst that is used for synthesizing dimethyl oxalate is characterized in that, selects for use IB, VB family, VIII family metallic element to make catalytic active component, is formulated as steeping liq, then in type carrier A l2O3 is put into maceration extract and makes; Preparation process is as follows: according to the load capacity of catalyst activity metal component and auxiliary agent, select nitrate, the niobium oxide (Nb of palladium (Pd), silver (Ag) for use
2O
5), nitric acid and water is mixed with maceration extract; Then carrier A l with loose structure
2O
3Soaked 1～10 hour, and after fully absorbing, isolated the immersion solid, again solid is carried out drying, 300～600 ℃ through roasting in 3～8 hours, just can be made into catalyst.
2, catalyst as claimed in claim 1 is characterized in that, selected IB family metallic element is preferably Ag, and VB family metallic element is preferably Nb, and VIII family metallic element is preferably Pd.
3, catalyst as claimed in claim 1 is characterized in that, metal element A g content is 0.1～2.0% of vehicle weight, and metallic element Nb content is 0.05～1.0% of vehicle weight, and metallic element Pd content is 0.05～1.0% of vehicle weight.
4, catalyst as claimed in claim 1 is characterized in that, used carrier A l
2O
3Be that specific area is 100～300m
2γ-Al of/g
2O
3
5, a kind of synthetic reaction of dimethyl oxalate is characterized in that, at Ag-Nb-Pd/Al
2O
3Under the effect of catalyst, make CO and methyl nitrite gas phase catalysis synthesizing dimethyl oxalate.Fixed-bed reactor is adopted in this reaction, reaction tube is the stainless steel tube of internal diameter 15mm, long 500mm, in adorn 5～100ml catalyst, the glass pellet 50mm that diameter 3mm is adorned at the catalyst layer top in addition is thick, reaction tube adopts the tube furnace heating, and its course of reaction is as follows: earlier CO, methyl nitrite and nitrogen are made into admixture of gas by the volume ratio of 2:1:7; The mist that will prepare then feeds reactor, and unstripped gas feed volume air speed is 1000～4000h
-1, 50～150 ℃ of reaction temperature controls, product is separated after condensation.
6, the synthetic reaction of dimethyl oxalate as claimed in claim 5 is characterized in that, the feed volume air speed of material mixed gas is 2000～3000h
-1
7, the synthetic reaction of dimethyl oxalate as claimed in claim 5 is characterized in that, the catalytic reaction temperature is 90～120 ℃.
8, want the synthetic reaction of 5 described dimethyl oxalates as right, it is characterized in that, catalytic reaction pressure is 0～0.2MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008101766737A CN101462081A (en) | 2008-10-25 | 2008-10-25 | Method for preparing catalyst for synthesizing dimethyl oxalate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008101766737A CN101462081A (en) | 2008-10-25 | 2008-10-25 | Method for preparing catalyst for synthesizing dimethyl oxalate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101462081A true CN101462081A (en) | 2009-06-24 |
Family
ID=40803011
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2008101766737A Pending CN101462081A (en) | 2008-10-25 | 2008-10-25 | Method for preparing catalyst for synthesizing dimethyl oxalate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101462081A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102649057A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Catalyst for preparing oxalate through coupling reaction of CO (carbon monoxide) |
| CN102872767A (en) * | 2012-10-23 | 2013-01-16 | 上海戊正工程技术有限公司 | Industrialized plate type reactor for carbonylating and coupling to synthesize ester |
-
2008
- 2008-10-25 CN CNA2008101766737A patent/CN101462081A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102649057A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Catalyst for preparing oxalate through coupling reaction of CO (carbon monoxide) |
| CN102649057B (en) * | 2011-02-25 | 2015-01-07 | 中国石油化工股份有限公司 | Catalyst for preparing oxalate through coupling reaction of CO (carbon monoxide) |
| CN102872767A (en) * | 2012-10-23 | 2013-01-16 | 上海戊正工程技术有限公司 | Industrialized plate type reactor for carbonylating and coupling to synthesize ester |
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| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
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| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20090624 |