CN1030366A - Silver on porous microsphere catalyst - Google Patents
Silver on porous microsphere catalyst Download PDFInfo
- Publication number
- CN1030366A CN1030366A CN88103163A CN88103163A CN1030366A CN 1030366 A CN1030366 A CN 1030366A CN 88103163 A CN88103163 A CN 88103163A CN 88103163 A CN88103163 A CN 88103163A CN 1030366 A CN1030366 A CN 1030366A
- Authority
- CN
- China
- Prior art keywords
- silver
- tiny balloon
- silver catalyst
- catalyst
- porose
- 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
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 40
- 239000004332 silver Substances 0.000 title claims abstract description 40
- 239000003054 catalyst Substances 0.000 title claims abstract description 25
- 239000004005 microsphere Substances 0.000 title description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000005245 sintering Methods 0.000 claims abstract description 7
- 238000005469 granulation Methods 0.000 claims abstract description 4
- 230000003179 granulation Effects 0.000 claims abstract description 4
- 238000011068 loading method Methods 0.000 claims abstract description 3
- 238000005554 pickling Methods 0.000 claims abstract description 3
- 239000002245 particle Substances 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 2
- 108010010803 Gelatin Proteins 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 230000001627 detrimental effect Effects 0.000 claims description 2
- 229910001447 ferric ion Inorganic materials 0.000 claims description 2
- 229920000159 gelatin Polymers 0.000 claims description 2
- 239000008273 gelatin Substances 0.000 claims description 2
- 235000019322 gelatine Nutrition 0.000 claims description 2
- 235000011852 gelatine desserts Nutrition 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims 1
- 230000008021 deposition Effects 0.000 claims 1
- 239000008187 granular material Substances 0.000 claims 1
- 239000011159 matrix material Substances 0.000 claims 1
- 238000005201 scrubbing Methods 0.000 claims 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 27
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 230000009466 transformation Effects 0.000 abstract description 6
- 238000006356 dehydrogenation reaction Methods 0.000 abstract description 2
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- 238000006757 chemical reactions by type Methods 0.000 abstract 1
- 150000003378 silver Chemical class 0.000 abstract 1
- 230000009885 systemic effect Effects 0.000 abstract 1
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 6
- 239000004575 stone Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 3
- 229910001961 silver nitrate Inorganic materials 0.000 description 3
- 238000011109 contamination Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- OMBRFUXPXNIUCZ-UHFFFAOYSA-N dioxidonitrogen(1+) Chemical compound O=[N+]=O OMBRFUXPXNIUCZ-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000008262 pumice Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 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
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
Abstract
A kind of loading type silver catalyst that is used for Formaldehyde Production.Adopt porose shell tiny balloon, make carrier, carry silver then through operations such as repeatedly pickling, granulation and sintering.Its silver content is 30～80%, specific surface area 0.7～1.1m
2/ g, air speed is 20000～100000 hours, is used for making formaldehyde from the methanol oxidation dehydrogenation, and its transformation efficiency is 90～98%, and yield is 78～85%, and selectivity is 80～90%, can work below 900 ℃, its formaldehyde quality can reach the above requirement of top grade product.The existing heatproof of this silver catalyst, systemic resistance is low, anti-pollution, can stand the repeatedly ballistic advantage of start-stop car, the transformation efficiency height is arranged again, the norm quota of consumption is low, improve characteristics such as throughput, be applicable to that silver does the reaction type of catalyst component oxydehydrogenation, be specially adapted to Formaldehyde Production.
Description
The present invention relates to a kind of silver catalyst that is used for Formaldehyde Production.
Common silver-colored method technology is to produce formaldehyde with the methanol oxidation dehydrogenation.Comparatively general silver catalyst has two kinds at present: a kind of is electrolytic silver (silver content is 99.99%), is characterized in the transformation efficiency height, and selectivity is good, and unit consumption is low etc.But there is contamination resistance poor, the easy-sintering inactivation, the life-span is short, the impact that is unable to undergo repeatedly to stop, weakness such as consuming electric power height during regeneration reducing.Another kind is a float stone silver, and it adopts natural pumice to make carrier, and silver carrying amount is about 40%, is a kind of loading type silver catalyst, and its major advantage is that stain resistance is strong, stands the repeatedly impact of start-stop car, and resistance to elevated temperatures is good, and regeneration reducing is simple, and energy consumption is low.Weakness is that transformation efficiency is low, and the unit consumption height is so production cost is higher.
The silver catalyst that the present invention proposes has the advantage of above-mentioned two kinds of silver catalysts concurrently, has overcome the weakness of above-mentioned two kinds of silver catalysts to a certain extent.Its catalytic activity is silver-colored stronger than float stone, and contamination resistance is strong, stands the repeatedly impact of start-stop car, can work below 900 ℃, is a kind of comparatively ideal catalyzer.
Silver catalyst of the present invention is a kind of loaded catalyst, adopts silver attached on the inert support.The material of its carrier can be various potteries, as silico-aluminate, aluminum oxide, diatomite or the like.Carrier is made up of porose shell tiny balloon.On the porose shell tiny balloon spheroid a plurality of holes can be arranged, its hole can be perforation, also can be closed pores.The loose density of this porose shell tiny balloon powder is 0.2～0.5g/cm
3Particle diameter is 20～100 μ.With the loose density is 0.3g/cm
3, particle diameter 20～80 μ are advisable.
Making of porose shell tiny balloon need be removed mechanical impurity earlier, carries out repeatedly pickling then, and detrimental impurity such as iron, sodium, potassium and calcium etc. are removed in dissolving.Wherein the remaining amount of ferric ion should be below 0.015%.And make porose shell tiny balloon surfaces externally and internally coarse, to increase the sticking power of argent on carrier and to increase the effective surface area of its reaction.Porose shell tiny balloon after the purification adds yellow soda ash; one class fusing assistant such as boric acid; add-on is 16～22%(weight) and the tackiness agent of a class such as gelatin solution; concentration is 2～4%(weight), mix and be mixed evenly, make granular with fashion of extrusion; place tablets press internal rotation rolling balling; particle diameter is 2～4mm oven dry, sieves the specification that becomes to vary in size, in order to thermal sintering.
Particle through granulation formation, under a little less than the Tamman temperature, carry out sintering, make solid particles surface ion, atom or molecule begin to move, surface tissue changes intensely, unsettled surface disappears, generate the new surface of stability, thereby improved the physical strength of carrier, still keep the structure of microballoon hollow again.
The carrier that sinters, its loose density are 0.2～0.5g/cm
3Specific surface area is 0.7～1.7M
2/ g, vesicularity is 55～65%, chemical stability is 0.3～0.6%.
Above-mentioned carrier is put into silver salt solution and is flooded behind the gas that adsorbs inside and outside the hole of draining.With the Silver Nitrate is example, require silver nitrate solution deep and thorough in the pore structure of carrier, reach and carry silver evenly, oven dry then 700 ℃ of temperature calcinings, allows Silver Nitrate decompose, be incubated 2～2.5 hours and eliminate nitrogen peroxide, crystallization is gone out on the pore structure surfaces externally and internally of argent attached to carrier, and its silver content is 30～80%, is about 60% to be advisable with silver content.
The formaldehyde that adopts silver catalyst of the present invention to produce, its quality product can reach the technical requirement of top grade product.Its transformation efficiency is 90～98%, and yield is 78～85%, and selectivity is 80～90%, can work below 900 ℃.
Following table is the silver catalyst that float stone silver and the present invention make, the contrast of catalytic activity:
Float stone silver and silver catalyst catalytic activity of the present invention
| The project catalyst type | Silver content % | Air speed hour | Transformation efficiency % | Yield % | Selectivity % | Remarks |
| Float stone silver | 38－40％ | 16684 | 84.82 | 65.40 | 77.40 | Data are got the high, normal, basic mean value of test |
| Silver catalyst of the present invention | 57.5～60 | 23713 | 95.02 | 79.26 | 84.90 | Data are got the high, normal, basic mean value of test |
The silver catalyst that adopts the present invention to make has been to use 1 year on 12000 tons of equipment in the formaldehyde annual production, and comparing 1. quality producies with float stone silver all is the top grade product; 2. 500 tons of methyl alcohol save material; 3. calculate by air speed and can increase production 3000～3600 tons in formaldehyde.
Claims (6)
1, a kind of loading type silver catalyst adopts deposition of silver on inert support, it is characterized in that inert support is made up of porose shell tiny balloon, and its loose density is 0.2～0.5g/cm
3, the particle diameter of porose shell tiny balloon is 20～80 μ.
2, according to the described silver catalyst of claim 1, it is characterized in that the hole on the porose shell tiny balloon spheroid can be perforation, also can be closed pores, and on a tiny balloon, can be a plurality of holes.
3, according to the described silver catalyst of claim 1, it is characterized in that porose shell tiny balloon, need be through repeatedly pickling, make porose shell tiny balloon surfaces externally and internally long-pending coarse, surface-area increases, dissolved removing such as detrimental impurity in the matrix such as iron, sodium, potassium and calcium, wherein the remaining amount of ferric ion is in 0.015%(weight) below.The qualified microballoon of acid-scrubbing cleaning adds yellow soda ash, and a class fusing assistant such as boric acid, its add-on is 16～22%(weight) and the tackiness agent of a class such as gelatin solution, concentration is 2～4%(weight), mix the even granulation balling-up that is mixed, make the granule of 2～4mm, oven dry is in order to sintering.
4, according to the described silver catalyst of claim 1, it is characterized in that porose shell tiny balloon after granulation, carries out sintering under a little less than the Tamman temperature, make it have certain mechanical strength, bigger specific surface area is arranged again.
5, according to the described silver catalyst of claim 1, it is characterized in that the carrier behind the thermal sintering, immerse silver salt, the oven dry calcining is decomposed silver salt then, and argent is attached to the surfaces externally and internally of porose shell tiny balloon, its silver content 30～80%.
6, according to the described silver catalyst of claim 1, the material that it is characterized in that porose shell tiny balloon can be various potteries, as silico-aluminate aluminum oxide and diatomite or the like.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN88103163A CN1030366A (en) | 1988-05-23 | 1988-05-23 | Silver on porous microsphere catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN88103163A CN1030366A (en) | 1988-05-23 | 1988-05-23 | Silver on porous microsphere catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1030366A true CN1030366A (en) | 1989-01-18 |
Family
ID=4832478
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN88103163A Pending CN1030366A (en) | 1988-05-23 | 1988-05-23 | Silver on porous microsphere catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1030366A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102274722A (en) * | 2011-06-17 | 2011-12-14 | 中国科学院福建物质结构研究所 | V2O3 for preparing anhydrous formaldehyde by directly dehydrogenizing methanol as well as supported V2O3 catalyst and preparation method thereof |
-
1988
- 1988-05-23 CN CN88103163A patent/CN1030366A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102274722A (en) * | 2011-06-17 | 2011-12-14 | 中国科学院福建物质结构研究所 | V2O3 for preparing anhydrous formaldehyde by directly dehydrogenizing methanol as well as supported V2O3 catalyst and preparation method thereof |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |