CN101811064A - Method for preparing composite catalyst for phosphine multi-phase oxidation - Google Patents
Method for preparing composite catalyst for phosphine multi-phase oxidation Download PDFInfo
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- CN101811064A CN101811064A CN201010145177A CN201010145177A CN101811064A CN 101811064 A CN101811064 A CN 101811064A CN 201010145177 A CN201010145177 A CN 201010145177A CN 201010145177 A CN201010145177 A CN 201010145177A CN 101811064 A CN101811064 A CN 101811064A
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- nitrate
- filter cake
- phosphine
- carrier
- distilled water
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- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 239000003054 catalyst Substances 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 19
- 239000002131 composite material Substances 0.000 title claims abstract description 13
- 229910000073 phosphorus hydride Inorganic materials 0.000 title claims abstract description 12
- 230000003647 oxidation Effects 0.000 title claims abstract description 9
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 9
- 239000012153 distilled water Substances 0.000 claims abstract description 21
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 15
- 239000012065 filter cake Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000012216 screening Methods 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- 238000005406 washing Methods 0.000 claims description 13
- 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 claims description 10
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- 238000007654 immersion Methods 0.000 claims description 5
- 238000005245 sintering Methods 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims 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 claims description 4
- 240000007594 Oryza sativa Species 0.000 claims description 3
- 235000007164 Oryza sativa Nutrition 0.000 claims description 3
- 235000009566 rice Nutrition 0.000 claims description 3
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 3
- 239000010457 zeolite Substances 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 238000006424 Flood reaction Methods 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- 238000009413 insulation Methods 0.000 claims description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 27
- 238000010521 absorption reaction Methods 0.000 abstract description 16
- 239000007789 gas Substances 0.000 abstract description 8
- 239000012535 impurity Substances 0.000 abstract description 3
- 239000002440 industrial waste Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- 238000001816 cooling Methods 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 229910001960 metal nitrate Inorganic materials 0.000 abstract 1
- 238000002791 soaking Methods 0.000 abstract 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 19
- 229910052698 phosphorus Inorganic materials 0.000 description 17
- 239000011574 phosphorus Substances 0.000 description 17
- 229960002163 hydrogen peroxide Drugs 0.000 description 13
- 239000007788 liquid Substances 0.000 description 13
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 11
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 4
- 239000002912 waste gas Substances 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 3
- 239000000920 calcium hydroxide Substances 0.000 description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 3
- 239000012159 carrier gas Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 240000002234 Allium sativum Species 0.000 description 1
- -1 Hydrogen Chemical class 0.000 description 1
- 208000005374 Poisoning Diseases 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000004611 garlic Nutrition 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Abstract
The invention relates to a method for preparing a composite catalyst for phosphine multi-phase oxidation, which belongs to the technical field of industrial waste gas purification treatment. The method comprises the following steps: dissolving over two metal nitrates into distilled water to form composite metal ion solution; pre-treating a carrier, soaking the carrier into the metal ion solution with stirring, filtering the solution to obtain a filter cake, and drying the filter cake; placing the dried filter cake in a roasting furnace to perform roasting; and cooling and screening the roasted filter cake to obtain a catalyst product. The method is convenient and quick; and the prepared composite catalyst can obviously improve the absorption efficiency of hydrogen peroxide solution on phosphine, has good stability, no impurity and little using amount, and can be repeatedly used.
Description
Technical field
The present invention relates to a kind of method for preparing composite catalyst that is used for phosphine multi-phase oxidation, belong to the industrial waste gas purifying processing technology field.
Background technology
In phosphorus production, can produce a kind of waste residue of forming by element phosphor, dust impurity and water-mud phosphorus.In order to reclaim the phosphorus in the mud phosphorus, studies show that adopting mud phosphorus and alkaline reaction to produce sodium hypophosphite is a kind of effective governing measure, its reaction temperature is not high, energy resource consumption is little, and sodium hypophosphite is as a kind of reducing agent, be widely used in industries such as chemical plating, plating, machinery, food processing, have higher economic value added.But this improvement method will make in the mud phosphorus about 20% phosphorus simple substance be converted into hydrogen phosphide and enter into tail gas, if it is not handled, then can cause atmosphere pollution.
Hydrogen phosphide is colourless, garlic smell is arranged.But as be mixed with a small amount of poly-hydrogen phosphide spontaneous combustion, can blast when concentration acquires a certain degree, hydrogen phosphide has strong reducing property, can with many oxidant reduction reactions, as KMnO
4, I
2Hydrogen phosphide has hypertoxicity, when phosphine concentration is 10mgm
-3The time, human body contact 6h can have poisoning symptom.Concentration is 409～846mgm
-3The time, contact 0.5～1.0h can cause death.The method of purifying hydrogen phosphide is a lot of both at home and abroad, mainly is divided into two kinds of dry method and wet methods.The selection of various purification methods is decided according to the character and the source of waste gas, and the phosphine waste gas low for concentration, that total amount is few often adopts absorption method; Big normal employing absorbs oxidizing process and reclaims wherein phosphor resource for concentration height, total amount.
It is higher that mud phosphorus is produced the phosphine waste gas concentration that sodium hypophosphite produces, be fit to adopt hydrogenperoxide steam generator as absorption liquid, make the hydrogen phosphide in the tail gas be oxidized to sodium hypophosphite with absorbing this waste gas of oxidative treatment, thereby increase the output of sodium hypophosphite product, resource is rationally utilized.Find in the practical application, absorb hydrogen phosphide tail gas,, make absorption efficiency on the low side because its reaction speed is slower with hydrogen peroxide.Therefore, must add catalyst and come fast reaction speed, improve absorption efficiency.
Summary of the invention
The purpose of this invention is to provide a kind of method for preparing composite catalyst that is used for phosphine multi-phase oxidation, multiple metal ion has synergy, solidification, peptizaiton in the prepared catalyst, can improve the catalytic efficiency and the stability of catalyst, can obviously improve the absorption efficiency of hydrogenperoxide steam generator to hydrogen phosphide, and catalyst amount is less, and is reusable.
The present invention is achieved through the following technical solutions: two or more nitrate are dissolved in the distilled water, are made into metal ion solution; Carrier carries out preliminary treatment earlier, is immersed in the metal ion solution under stirring then, filters and obtains filter cake, again oven dry; Place roaster to synthesize dried filter cake, obtain catalyst prod.
Concrete technical scheme of the present invention is:
(1) nitrate adopts be in ferric nitrate, copper nitrate, zinc nitrate, silver nitrate, the cerous nitrate more than two kinds,, the metal ion solution concentration that is made into is 0.01～1mol/L; (2) carrier is any in granularity 40～180 purpose powdery zeolites, diatomite, active carbon, activated alumina, the rice hull ash; (3) flood in the metal ion solution that carrier 1: 5 by volume～30 addings prepare; (4) sintering temperature of roaster is that 250～800 ℃, insulation synthesized in 2～6 hours, obtains catalyst through screening then.
In the NaOH of 0.1mol/L solution, soaked 1 hour earlier during the carrier preliminary treatment, use the distilled water cyclic washing then, the HCl solution with 0.1mol/L soaked 1 hour again, soaked back distilled water cyclic washing, used distilled water immersion at last 1 hour, and filtered the back and dry 12h down at 105～130 ℃; Carrier impregnation is to stir at normal temperatures 4～6 hours, floods then 18～20 hours, filters at last, obtains filter cake and dries 1～3 hour again.
The present invention has the following advantages:
(1) add catalyst of the present invention, hydrogenperoxide steam generator obviously improves the absorption efficiency of hydrogen phosphide;
(2) have synergy, solidification, peptizaiton between each metal ion of composite catalyst, the composite catalyst stability that makes better with solid-state adding, is not brought other impurity into;
(3) the composite catalyst consumption is less, and reusable.
Description of drawings:
Fig. 1 is the process chart of invention Preparation of Catalyst;
Fig. 2 is an invention hydrogen phosphide heterogeneous catalytic oxidation process chart;
Fig. 3 is the assimilation effect figure of invention example 1;
Fig. 4 is the assimilation effect figure of invention example 2;
Fig. 5 is the assimilation effect figure of invention example 3.
The specific embodiment:
Example 1: ferric nitrate, cerous nitrate are dissolved in the distilled water with mol ratio at 1: 1, are made into the solution that concentration of metal ions is 0.01mol/L; With particle diameter is 180 purpose 4A zeolites, in the sodium hydroxide solution of 0.1mol/L, soaked 1 hour, soak the back repeatedly with the distilled water cyclic washing, hydrochloric acid solution with 0.1mol/L soaked 1 hour again, soak the back repeatedly with the distilled water cyclic washing, used distilled water immersion at last 1 hour, and filtered the back and dried 12 hours down at 105 ℃; Through after the preliminary treatment, add at 1: 5 in the solution for preparing according to the solid-liquid mass ratio, normal temperature stirred 4 hours down, flooded then 20 hours, filtered at last; Filter cake after the oven dry is placed roaster, and sintering temperature is 250 ℃, is incubated 6 hours, and screening obtains 180 purpose catalyst; The catalyst that makes is added in hydrogenperoxide steam generator with mass ratio at 1: 200.The material of reactor is mud phosphorus 10.01g (phosphorus content 45.2%), alkali lye 180mL (containing NaOH 7.26g, calcium hydroxide 1.43g) during the preparation sodium hypophosphite; Carrier gas is a nitrogen, and flow velocity is 20mL/min; Gas washing liquid is selected 85% SPA 100mL for use; Absorption liquid is 6% hydrogenperoxide steam generator 100mL, and to regulate the absorption liquid pH value with the 0.1mol/L sodium hydroxide solution be 14.
Hydrogenperoxide steam generator is seen Fig. 3 to the assimilation effect of hydrogen phosphide, and sodium hypophosphite output is 1.4587g behind the absorption 6h, and the conversion ratio of phosphorus is 47.14%.
Example 2: ferric nitrate, zinc nitrate, copper nitrate are dissolved in the distilled water with mol ratio at 2: 1: 1, are made into the solution that concentration of metal ions is 0.5mol/L; With particle diameter is 110 purpose rice hull ash, in the sodium hydroxide solution of 0.1mol/L, soaked 1 hour, soak the back repeatedly with the distilled water cyclic washing, hydrochloric acid solution with 0.1mol/L soaked 1 hour again, soak the back repeatedly with the distilled water cyclic washing, used distilled water immersion at last 1 hour, and filtered the back and dried 12 hours down at 118 ℃; Through after the preliminary treatment, add at 1: 18 in the solution for preparing according to the solid-liquid mass ratio, normal temperature stirred 5 hours down, flooded 19 hours, filtered at last; Filter cake after the oven dry is placed roaster, and sintering temperature is 525 ℃, is incubated 4 hours, and screening obtains 110 purpose catalyst; The catalyst that makes is added in hydrogenperoxide steam generator with mass ratio at 1: 100.The material of reactor is mud phosphorus 10.05g (phosphorus content 45.3%), alkali lye 175mL (containing NaOH 7.22g, calcium hydroxide 1.44g) during the preparation sodium hypophosphite; Carrier gas is a nitrogen, and flow velocity is 20mL/min; Gas washing liquid is selected 85% SPA 100mL for use; Absorption liquid is 6% hydrogenperoxide steam generator 100mL, and to regulate the absorption liquid pH value with sodium hydroxide solution be 13.
Hydrogenperoxide steam generator is seen Fig. 4 to the assimilation effect of hydrogen phosphide, and sodium hypophosphite output is 1.2356g behind the absorption 6h, and the conversion ratio of phosphorus is 39.69%.
Example 2: with ferric nitrate, cerous nitrate, silver nitrate, copper nitrate with mol ratio 4: 4: 1: 2 are dissolved in the distilled water, are made into the solution that concentration of metal ions is 1mol/L; With particle diameter is 40 purpose active carbons, in the sodium hydroxide solution of 0.1mol/L, soaked 1 hour, soak the back repeatedly with the distilled water cyclic washing, hydrochloric acid solution with 0.1mol/L soaked 1 hour again, soak the back repeatedly with the distilled water cyclic washing, used distilled water immersion at last 1 hour, and filtered the back and dried 12 hours down at 130 ℃; Through after the preliminary treatment, add at 1: 30 in the solution for preparing according to the solid-liquid mass ratio, normal temperature stirred 6 hours down, flooded 18 hours, filtered at last; Filter cake after the oven dry is placed roaster, and sintering temperature is 800 ℃, is incubated 2 hours, and screening obtains 40 purpose catalyst; The catalyst that makes is added in hydrogenperoxide steam generator with mass ratio at 1: 100.The material of reactor is mud phosphorus 9.98g (phosphorus content 45.3%), alkali lye 175mL (containing NaOH 7.22g, calcium hydroxide 1.44g) during the preparation sodium hypophosphite; Carrier gas is a nitrogen, and flow velocity is 20mL/min; Gas washing liquid is selected 85% SPA 100mL for use; Absorption liquid is 6% hydrogenperoxide steam generator 100mL, and to regulate the absorption liquid pH value with sodium hydroxide solution be 13.
Hydrogenperoxide steam generator is seen Fig. 5 to the assimilation effect of hydrogen phosphide, and sodium hypophosphite output is 1.2034g behind the absorption 6h, and the conversion ratio of phosphorus is 38.92%.
Claims (3)
1. a method for preparing composite catalyst that is used for phosphine multi-phase oxidation is characterized in that: two or more nitrate are dissolved in the distilled water, are made into metal ion solution; Carrier carries out preliminary treatment earlier, is immersed in the metal ion solution under stirring then, filters and obtains filter cake, again oven dry; Place roaster to synthesize dried filter cake, obtain catalyst prod.
2. by the described method for preparing composite catalyst that is used for phosphine multi-phase oxidation of claim 1, it is characterized in that: (1) nitrate adopts be in ferric nitrate, copper nitrate, zinc nitrate, silver nitrate, the cerous nitrate more than two kinds, the metal ion solution concentration that is made into is 0.01～1mol/L; (2) carrier is any in granularity 40～180 purpose powdery zeolites, diatomite, active carbon, activated alumina, the rice hull ash; (3) flood in the metal ion solution that carrier 1: 5 by volume～30 addings prepare; (4) sintering temperature of roaster is that 250～800 ℃, insulation synthesized in 2～6 hours, obtains catalyst through screening then.
3. by the described method for preparing composite catalyst that is used for phosphine multi-phase oxidation of claim 2, it is characterized in that: in the NaOH of 0.1mol/L solution, soaked 1 hour earlier during the carrier preliminary treatment, use the distilled water cyclic washing then, HCl solution with 0.1mol/L soaked 1 hour again, soak back distilled water cyclic washing, used distilled water immersion at last 1 hour, and filtered the back and dry 12h down at 105～130 ℃; Carrier impregnation is to stir at normal temperatures 4～6 hours, floods then 18～20 hours, filters at last, obtains filter cake and dries 1～3 hour again.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201010145177A CN101811064A (en) | 2010-04-13 | 2010-04-13 | Method for preparing composite catalyst for phosphine multi-phase oxidation |
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| CN201010145177A CN101811064A (en) | 2010-04-13 | 2010-04-13 | Method for preparing composite catalyst for phosphine multi-phase oxidation |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102240499A (en) * | 2011-07-15 | 2011-11-16 | 田琳 | Composite absorbing agent for processing hydrogen phosphide gas and preparation method thereof |
| CN111375291A (en) * | 2018-12-31 | 2020-07-07 | 中国石油化工股份有限公司 | Treatment method of sulfide-containing organic waste gas |
-
2010
- 2010-04-13 CN CN201010145177A patent/CN101811064A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| QIONGFEN YU ET AL.: "Study of PH3 Adsorption and Regeneration over CuO-ZnO-La2O3/Activated Carbon Adsorbents", 《POWER AND ENERGY ENGINEERING CONFERENCE(APPEEC),2010 ASIA-PACIFIC》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102240499A (en) * | 2011-07-15 | 2011-11-16 | 田琳 | Composite absorbing agent for processing hydrogen phosphide gas and preparation method thereof |
| CN102240499B (en) * | 2011-07-15 | 2013-06-12 | 田琳 | Composite absorbing agent for processing hydrogen phosphide gas and preparation method thereof |
| CN111375291A (en) * | 2018-12-31 | 2020-07-07 | 中国石油化工股份有限公司 | Treatment method of sulfide-containing organic waste gas |
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Application publication date: 20100825 |