CN1065153C - High-temperature shift catalyst and preparation method thereof - Google Patents
High-temperature shift catalyst and preparation method thereof Download PDFInfo
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- CN1065153C CN1065153C CN94113013A CN94113013A CN1065153C CN 1065153 C CN1065153 C CN 1065153C CN 94113013 A CN94113013 A CN 94113013A CN 94113013 A CN94113013 A CN 94113013A CN 1065153 C CN1065153 C CN 1065153C
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- 239000003054 catalyst Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 24
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 claims abstract description 19
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 15
- 230000008569 process Effects 0.000 claims abstract description 15
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 13
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 10
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001354 calcination Methods 0.000 claims abstract description 10
- 239000002245 particle Substances 0.000 claims abstract description 6
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims abstract description 5
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 5
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract 5
- 238000006243 chemical reaction Methods 0.000 claims description 36
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 32
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 31
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 28
- 238000001556 precipitation Methods 0.000 claims description 16
- 229910021529 ammonia Inorganic materials 0.000 claims description 14
- 239000000047 product Substances 0.000 claims description 12
- 238000000227 grinding Methods 0.000 claims description 11
- 230000009466 transformation Effects 0.000 claims description 9
- 239000011265 semifinished product Substances 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 6
- 238000013329 compounding Methods 0.000 claims description 6
- 238000005265 energy consumption Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 238000005469 granulation Methods 0.000 claims description 4
- 230000003179 granulation Effects 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims 2
- 241001504664 Crossocheilus latius Species 0.000 claims 1
- 229960004643 cupric oxide Drugs 0.000 claims 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 1
- 238000005096 rolling process Methods 0.000 claims 1
- 239000011787 zinc oxide Substances 0.000 claims 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 abstract description 19
- 238000001914 filtration Methods 0.000 abstract description 5
- 238000004062 sedimentation Methods 0.000 abstract description 5
- 239000002131 composite material Substances 0.000 abstract description 2
- 238000003825 pressing Methods 0.000 abstract description 2
- 238000007605 air drying Methods 0.000 abstract 1
- 229910000423 chromium oxide Inorganic materials 0.000 abstract 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 abstract 1
- 238000004806 packaging method and process Methods 0.000 abstract 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 abstract 1
- 229910001950 potassium oxide Inorganic materials 0.000 abstract 1
- 239000013049 sediment Substances 0.000 abstract 1
- 238000007873 sieving Methods 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 19
- 239000011651 chromium Substances 0.000 description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000007788 liquid Substances 0.000 description 13
- 239000007789 gas Substances 0.000 description 12
- 239000003337 fertilizer Substances 0.000 description 10
- 238000006722 reduction reaction Methods 0.000 description 10
- 230000009467 reduction Effects 0.000 description 9
- 230000008859 change Effects 0.000 description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- JJEJDZONIFQNHG-UHFFFAOYSA-N [C+4].N Chemical compound [C+4].N JJEJDZONIFQNHG-UHFFFAOYSA-N 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 230000001376 precipitating effect Effects 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000000975 co-precipitation Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 230000009183 running Effects 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000011010 flushing procedure Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000000618 nitrogen fertilizer Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229960004424 carbon dioxide Drugs 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 210000000952 spleen Anatomy 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- OBOXTJCIIVUZEN-UHFFFAOYSA-N [C].[O] Chemical compound [C].[O] OBOXTJCIIVUZEN-UHFFFAOYSA-N 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- IYRDVAUFQZOLSB-UHFFFAOYSA-N copper iron Chemical compound [Fe].[Cu] IYRDVAUFQZOLSB-UHFFFAOYSA-N 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- LITYQKYYGUGQLY-UHFFFAOYSA-N iron nitric acid Chemical compound [Fe].O[N+]([O-])=O LITYQKYYGUGQLY-UHFFFAOYSA-N 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 230000005226 mechanical processes and functions Effects 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000003643 water by type 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
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- Catalysts (AREA)
Abstract
The invention provides a novel high-temperature shift catalyst and a preparation method thereof, wherein the novel high-temperature shift catalyst is composed of 100 parts of ferric oxide, 2-9 parts of chromium oxide, 0.3-0.6 part of potassium oxide and an auxiliary agent. The preparation method comprises the steps of carrying out a neutralization reaction by fully parallel-flow of a ferrous nitrate solution, a chromic acid solution and an ammonium bicarbonate solution, and adding an auxiliary agent in the neutralization process to obtain a composite material with quick sediment sedimentation and easy filtration; adding the auxiliary agent solution into the dried material again, granulating, air-drying, calcining the particles, pressing into tablets (with the size of phi 6.0 +/-0.1 multiplied by 3.0 +/-0.1 and phi 9 multiplied by 5), drying, sieving and packaging to obtain the finished product.
Description
The invention belongs to and promote the carbon monodixe conversion reaction--high temperature conversion catalyst that carbon monoxide and steam reaction generation carbon dioxide and hydrogen are used and preparation method thereof.
For Preparation of catalysts technology, prescription and details, each state all holds in close confidence.The preparation method of existing carbon-oxide high-temperature conversion catalyst, employing be mechanical mixing, mix the precipitation method and coprecipitation.According to (volume such as catalysis teaching and research room of department of chemistry of Nanjing University, " temperature carbon monoxide shift catalyst ", 93～99 Chemical Industry Press, 1979; Volumes such as Xiang Dehui, " chemical fertilizer catalysis application manual ", 144～145, Chemical Industry Press, 1992) to introduce, mechanical mixing is with FeSO
47H
2O (liquid) is a raw material, and the carbon ammonium is made precipitating reagent, obtains semi-finished product and adds chromic anhydride auxiliary agent etc. through grinding material, obtains product behind the processing calcination tablet.Dust was big when this method was ground material, and the product quality fluctuation is bigger, and intensity descends big (just there is this problem in B109 type catalyst, and sheet burns and descends 20～30% before the back strength ratio is burnt) after the tablet calcination, catalyst sulfur content height.The mixed precipitation method are still with FeSO
47H
2O is a raw material, and carbon ammonium, ammoniacal liquor are made precipitating reagent, carries out reduction reaction with chromic anhydride after making the iron washing of precipitate, the gained semi-finished product after calcination, reprocess finished product.This method can be produced sulfur content and be lower than 0.06% catalyst, but the sulfate radical washing is difficult in the manufacture process, washing time many (more than 6 times), water consumption, consumption quantity of steam are big, and chromic anhydride reduction control fluctuation is bigger, in case reduction is not thorough, cause Cr VI to run off, influence the catalyst chemical component, and then influence product quality, cause chromium waste and contaminated environment simultaneously.(B110-2 type catalyst is exactly to produce with this method, also has these problems).The co-precipitation rule is earlier with FeSO
47H
2O liquid mixes with chromic anhydride, and carbon ammonium or ammoniacal liquor are made precipitating reagent, obtain semi-finished product, is processed into product through calcination etc.In manufacture process, exist the precipitation sedimentation slowly, easily to become colloid, flushing sulfate radical difficulty, filtration difficulty is difficult to make the low sulfur catalyst that contains.B107 type, B108 type, WB-2 type are all produced with this method.(" middle ammonia fertilizer " (supplementary issue) NO.1,55,1987; " middle nitrogenous fertilizer ", 2,60～61,1986; Volumes such as catalysis teaching and research room of department of chemistry of Nanjing University, " an oxygen carbon medium temperature shift catalyst ", 96, Chemical Industry Press, 1979; " chemical fertilizer and catalysis ", 3,37～40,1985).At present domestic also have producer to replace ferrous sulfate with ferrous nitrate, adopts coprecipitation to make high temperature conversion catalyst, and the B113 type promptly is.But exist filtration difficulty, material loss big equally, yield is low, only 50～60%.(" the Liao Dynastyization science and technology " NO.1,1988; " big ammonia fertilizer " 4,246,1987).(Dalian Polytechnic College is translated volume, " external synthetic catalyst data compilation ", 33,1977 according to interrelated data again; Zhao's gallop, " external catalyst performance handbook, 457, chemical fertilizer industry research institute of the Ministry of Chemical Industry information research chamber, 1984; ［ U.S. ］ A.V Si clarke etc., " synthetic ammonia ", second fascicle, 5～7, Chemical Industry Press, 1979; Volumes such as tail is rugged, " the catalyst handbook--press element classification ", 536～537, Chemical Industry Press, 1982) show that some catalyst manufacturing companies production high temperature conversion catalysts also are with FeSO abroad
4Be raw material, with NaOH or Na
2CO
3As precipitating reagent, adopt iron liquid and after chromic anhydride mixes again the coprecipitation of neutralization precipitation obtain.Along with day being becoming tight of world energy sources, various low energy consumption synthesis ammonia flow processs also occur in succession, but one of energy-conservation important measures are exactly to reduce primary reformer H in its flow process
2The O/C ratio.Because the reduction (H of primary reformer steam/hydrocarbons ratio
2O/
CThan below 3), this has just brought some problems to the shift conversion step behind the conversion procedure, and subject matter is to use traditional siderochrome base high conversion catalyst, at H
2O/
CLow more, when reaction temperature was high more, the amount of paying many carbon of reaction generation hydrocarbon of generation was also big more; The change furnace resistance drop is raise.In order to improve the performance of transformation catalyst, external ICI company, BASF AG, TOPS φ e company and SUd-Chemie company have released the siderochrome base high temperature transformation catalyst of cupric, as 71-3, the 71-4 type, the K6-11 type, SK-201, (LK-811, KK～142), C12-4/G-3C type, the catalyst of these models have effectively reduced the generation of hydro carbons by product, but when bigger fluctuation appears in process conditions, catalyst overcomes Fischer-Tropsch and pays the function of reaction and can be subjected to very big infringement and can not recover fully, transformation catalyst after the improvement, serviceability temperature is higher, and the K6-11 type is at low H
2O/
CDown, the change furnace inlet temperature is 330～340 ℃, the C12-4/G-3C type, and 320～330 ℃ of inlet temperatures, LK-811 and KK-142 be no iron-copper based catalyst, 350 ℃ of the former serviceability temperature upper limits, latter's operating temperature that suits is 380～410 ℃.The 71-3 that has that is used for the low energy consumption synthesis ammonia flow process at present, 71-4 and C12-4/G-3C model catalyst.(chemical fertilizer technology development center of the Ministry of Chemical Industry compiles, the operating experience of ICI low steam carbon ratio transformation catalyst, " chemical fertilizer information ", 1989; " big nitrogenous fertilizer ", 4,271,1990; " chemical fertilizer information " November nineteen ninety; Xiang Dehui etc., " chemical fertilizer catalyst application manual ", 446, Chemical Industry Press, 1992; Big nitrogenous fertilizer, 2,83-85,1994).At present domestic does not still have be applicable to and hang down H
2O/
C, the high temperature conversion catalyst used of low energy consumption synthesis ammonia flow process, and the domestic large-scale synthetic ammonia installation of now having introduced AMV, BRaun flow process, and the large-scale synthetic ammonia installation of the domestic introduction seventies, face the fact that reducing energy consumption (transformation system transformation) also needs this type of high temperature conversion catalyst.
The purpose of this invention is to overcome in the existing high temperature conversion catalyst preparation, and the precipitation sedimentation slowly, easily becomes colloidal substance, washing of precipitate difficulty (washing the sulfate radical difficulty), and the sedimentation and filtration difficulty, the low and existing high temperature conversion catalyst serviceability temperature of material yield is higher, at low H
2Under the O/C, behind high temperature to expense--entrust the inhibition ability drop of reaction, the catalyst thermal stability is poor, deficiencies such as anti-deactivation capacity difference; The invention provides a kind of can being applicable to and hang down H
2O/
C, in the low energy consumption large-sized synthetic ammonia process, the axial conversion type of furnace, can be applicable to that again low sulfur-bearing, the serviceability temperature of diameter of axle change furnace in the conversion type of furnace and similar middle-size and small-size ammonia factory is low, use low, the anti-boiling water performance of vapour/gas, anti-deactivation ability is good, can effectively be suppressed at low H
2Under the O/C, catalyst is by over reduction and expense--entrust the generation of reaction, activity stabilized high-temp transformation catalyst and preparation method thereof in the use.
Preparation method of the present invention is: with scrap iron that burnt and the reaction of nitric acid iron, its reaction is earlier:
Make ferrous nitrate solution; Chromic anhydride is mixed with chromic acid solution; With ammonium bicarbonate solution as precipitating reagent; Adopt ferrous nitrate liquid, chromic acid solution, three kinds of materials of ammonium bicarbonate solution and stream carry out neutralization-precipitation reaction, and add aluminium salt and obtain the fast composite precipitation thing of uniform sedimentation in N-process.Precipitation is filtered through flushing sheet frame filter--and dry that siderochrome is main semi-finished product; Adopt roller to mix and roll material.Grinding this operation of material, pressing semi-finished product and analyze Fe
2O
3, Cr
2O
3Content results, the metering, with addition of chromic acid solution, compounding agent solution and potassium hydroxide solution.Material after mixed grind carries out granulation, pneumatic conveying drying, calcination particle, mixing (add graphite, add water), beats sheet (tablet sizes φ 6 * 3, and φ 9 * 5), the baking sheet, sieve pack finished product.
In preparation process, the neutralization precipitation operation with ferrous nitrate liquid concentration (with Fe
23Fe is pressed in meter 140～180g/l) meterings
2O
3Be 100 (weight), with Cr
2O
3Meter 2～5 (weight) also are mixed with the solution of 5～20% concentration, neutralize, and add the aluminum nitrate (liquid or solid) of 0.3～1.5 (weight), 60～70 ℃ of control reaction temperatures, pH value 6.5～7.5, in and 2～2.5 hours time, neutralization finishes pH value 7.0; Grind material process and be metered into chromic acid solution with the semi-product material analysis result, compounding agent solution, KOH solution by weight, adds Fe earlier
2O
3100 parts, (cumulative amount is with Cr to add chromic acid liquid then
2O
3Meter) 2～9 parts, 1.5～5.0 parts of auxiliary agents (MO meter), auxiliary agent (M
1O) 0.5～4 part, KOH0.3～0.6 part adding, mix and rolled 45～65 minutes, then through granulation, pneumatic conveying drying, mix (adding the heavy graphite of 1.5～2.0% materials, 8～11% water) behind the calcination particle, be pressed into the tablet of φ 6.0 ± 0.1 * 3.0 ± 0.1 and φ 9 * 5 specifications, oven dry is sieved, is packed again.
Because the present invention has adopted with ferrous nitrate liquid, chromic acid solution and three kinds of materials of ammonium bicarbonate solution and has flowed even neutralization precipitation, and the adding aluminum nitrate prepares semi-finished product in the neutralization precipitation process, when grinding material, the secondary interpolation auxiliary agent of chromic acid liquid, compounding agent solution is allocated in metering into again, have liquid phase participate in down liquid--the interactional even mixing of solid phase rolls, beat the preparation method of sheet behind the employing calcination particle, the finished product that obtains in use, have easy reduction, use H
2O/ gas (doing) is than low, and the body sulfur-bearing is low, and reduction back intensity is good, and good anti-boiling water performance and anti-deactivation (property) ability are arranged, and serviceability temperature is low, at low H
2Under the O/C, can prevent the catalyst over reduction, the inhibition expense--entrust reaction, thereby in use advantages such as activity stabilized are arranged.The catalyst end product quality that obtains has obtained the approval of Switzerland Ka Sali system ammonia company (Ammonla Casale S.A), (physics of this catalyst and catalytic performance entrust ICI company to detect by Ka Sali system ammonia company) has been chosen to be Ka Sali system ammonia company Yun'nan Natural Gas Chemical Plant's transformation system reducing energy consumption--is transformed into the diameter of axle to the conversion type of furnace with the former axial change furnace type--high temperature conversion catalyst of usefulness.
Embodiment A is got ferrous nitrate concentration (Fe in actual mechanical process
2O
3Meter) 150g/l presses Fe
2O
3100 (weight), Cr
2O
34 (weight) take by weighing chromic anhydride, and to be mixed with concentration be 10% chromic acid solution, carbon ammonium concentration of lye 160g/l ((NH
4)
2CO
3Count), 60～64 ℃ of neutralization reaction temperature, iron liquid, alkali lye also flow earlier and add after 30 minutes, promptly open chromic acid liquid and cut down, and carry out neutralization-precipitation reaction with three kinds of materials and stream, and Fe are pressed in adding
2O
3The aluminum nitrate solid of gross weight 1.5%, pH value is controlled at 6.5～7.0; Precipitation after greater than 60 ℃ of desalted waters flushing 2 times, with the filtration of sheet frame filter, filter cake dry to moisture content less than 5% and analyze Fe
2O
3, Cr
2O
3Content, when grinding material, according to analysis result, successively by weight, Fe
2O
3100 parts, Cr
2O
36 parts, auxiliary agent MO are 2 parts of CuO, auxiliary agent M
1O is 0.5 part of ZnO, Al
2O
3Part 1.1 (no longer adding when grinding material), KOH0.4 part once adds.The Cr that need add
2O
3With chromic acid solution, with zinc nitrate solution, the form that reaches KOH solution adds CuO with copper nitrate solution, ZnO.Mix to press and grind after 50 minutes, behind granulation, pneumatic conveying drying calcination particle, be pressed into the tablet of Φ 6 * 3, Φ 9 * 5 specifications, obtain product catalyst A after dry the processing
Embodiment B ferrous nitrate concentration (Fe
2O
3Meter) 170g/l presses Fe
2O
3100 (weight), Cr
2O
32.6 (weight) takes by weighing chromic anhydride, be made into the chromic acid solution of concentration 5%, carbon ammonium concentration of lye 180g/l, 65～70 ℃ of neutralization reaction temperature, in iron liquid, alkali lye and the stream and open chromic acid solution control after 20 minutes and cut down, carry out neutralization reaction with the complete also stream of three kinds of logistics, and Fe is pressed in adding in the neutralization reaction process
2O
3The aluminum nitrate of gross weight 1%, (the solution form that is made into 10% weight concentration adds with other three kinds of materials and stream), pH value 7.0～7.5; Before grinding material, analyze baking railway carriage or compartment material Fe
2O
3, Cr
2O
3Content, and successively by weight, Fe
2O
3100 parts, Cr
2O
34 parts, 4 parts of auxiliary agent MO, M
12.5 parts of O, Al
2O
3Part 0.8 (no longer adding when grinding material), KOH once adds for 0.6 part; Add Cr
2O
3Reaching CuO, ZnO, KOH adds with chromic acid solution, copper nitrate solution, zinc nitrate solution, KOH solution form respectively.Other preparation process gets finished catalyst B at last with (example one)
Embodiment C is got ferrous nitrate concentration (Fe
2O
3Meter) 140g/l presses Fe
2O
3(weight) 100, Cr
2O
3(weight) 5, take by weighing chromic anhydride, and to be made into concentration be 15% chromic acid solution, carbon ammonium concentration of lye 150g/l﹠amp; #60 (NH
4)
2CO
3Meter ﹠amp; #62,62～66 ℃ of neutralization reaction temperature, iron liquid, alkali lye, chromic acid solution and stream adding carrying out precipitation reaction, and Fe is pressed in adding
2O
3The aluminum nitrate solid of gross weight 0.8%, pH value 6.5～7.0; Analyze Fe according to the oven dry semi-finished product when grinding material
2O
3, Cr
2O
3Content, by weight: Fe
2O
3100 parts, Cr
2O
38 parts, 3 parts of auxiliary agent MO, auxiliary agent M
11.5 parts of O, Al
2O
3Part 0.5 (no longer adding when grinding material), 0.5 part of order of KOH once adds; Need the Cr of adding
2O
3, CuO, ZnO, KOH add with chromic acid solution, copper nitrate solution, zinc nitrate solution and KOH solution form respectively, all the other preparation process are identical with embodiment one, finally obtain catalyst prod C
Press the performance test of catalyst A, B, C and the C12-4 type (U.S.'s product) of the present invention's preparation.The results are shown in table one to table five
From measurement result, the performance of catalyst that the present invention obtains is better than C12-4 type (U.S.'s product)
Table one, catalyst A and C12-4 type low temperature active
| Reaction temperature (℃) | Air speed (h -1) | A | The C12-4 type | Remarks |
| 350 | 1000 1500 2200 | 92．5 91．8 88．9 | 83．4 78．1 69．2 | Condition determination: normal pressure, H 2It is that riverization two is changed factory's second stage exit gas that O/ gas (thousand)=0.97 is measured with unstripped gas |
| 300 | 1000 1500 2200 | 79．4 70．9 59．8 | 38．3 31．5 25．3 | |
| 250 | 1000 1500 2200 | 31．0 23．9 17．5 | 8．6 7．5 6．8 |
Table two, A, B, C, D and C12-4 type hang down H
2Activity under the O/ gas
Remarks: condition determination: normal pressure, unstripped gas are that riverization two change factory secondary reformers are worked off one's feeling vent one's spleen.
| Reaction temperature (℃) | H 2O/ gas (thousand) | Air speed (h -1) | C12-4 | A | B | C |
| 323 | 0．35 | 1000 1500 2200 | 70．1 63．9 57．5 | 76．2 70．2 63．8 | 77．2 72．4 65．4 | 73．6 67．5 61．4 |
| 323 | 0．43 | 1000 1500 2200 | 72．3 66．4 59．8 | 77．6 73．1 65．2 | 78．5 73．4 66．3 | 77．7 71．5 64．4 |
Table three, A, B, C and C12-4 type heat resistance are measured
Annotate: condition determination; Normal pressure, H
2O/ gas (doing)=0.97, unstripped gas are that riverization two chemical fertilizer factory's secondary reformers are worked off one's feeling vent one's spleen, 500 ℃ of heat resisting temperatures, permanent 20 hours.
| Reaction temperature (℃) | Air speed (h-1) | C12-4 | A | B | C |
| 348 | 1000 1500 2200 | 84．0 79．1 71．3 | 85．1 82．2 78．1 | 87．8 85．9 81．6 | 85．8 82．5 78．2 |
| Heat-resisting back 348 | 1000 1500 2200 | 64．1 55．7 | 76．8 59．5 | 84．2 78．9 70．4 | 80．7 73．6 66．8 |
Activity under table four, the different condition
| Reaction temperature (℃) 348 | H2O/ gas (doing) 0.69 | Air speed (h -1) 1,000 1,500 2200 | C12-4 75.4* 71.7* 66.1* | A 82.2 △ 78.0 △ 70.0 △ | Remarks *: be that 426 ℃ of fortune Zhi change measured value when dropping to 348 ℃ after 30 hours.*: from room temperature heating reduction again, measured value in the time of 383 ℃.△: be that 448 ℃ of runnings dropped to 348 ℃ of measured values after 30 hours.☆: be 448 ℃ the running 30 hours/after, drop to 348 ℃, move and be raised to 383 ℃ of measured values after 25 days again. |
| 383 | 0.35 | 1000 1500 2200 | 66.5** 66.0** 65.4** | 75.4☆ 71.0☆ 71.3☆ | |
| 395 | 0.69 0.48 | 1000 1500 2200 1500 | 77.3 77.4 77.1 70.9 | 83.0☆ 82.8☆ 82.3☆ 75.4 | |
| 426 426 | 0.35 0.69 | 1000 1500 2200 | 50.1 50.6 70.6 | 59.7 54.3 76.1 |
Activity under table four, the different condition
| Reaction temperature (℃) | H2O/ gas (doing) | Air speed (h -1) | C12-4 | A | Remarks |
| 348 | 0.69 | 1,000 1,500 2200 | 75.4* 71.7* 66.1* | 82.2 △ 78.0 △ 70.0 △ | *: be that 426 ℃ of fortune Zhi change measured value when dropping to 348 ℃ after 30 hours.* *: from room temperature heating reduction again, measured value in the time of 383 ℃.△: be that 448 ℃ of runnings dropped to 348 ℃ of measured values after 30 hours.☆: be that 48 ℃ of runnings are after 30 hours, drop to 348 ℃, move and be raised to 383 ℃ of measured values after 25 days again. |
| 383 | 0.35 0.69 | 1000 1500 2200 1000 1500 2200 | 66.5** 66.0** 65.4** 77.3 77.4 77.1 | 75.4☆ 71.0☆ 71.3☆ 83.0☆ 82.8☆ 82.3☆ | |
| 395 426 | 0.48 0.35 | 1500 1000 1500 | 70.9 50.1 50.6 | 75.4 59.7 54.3 | |
| 426 | 0.69 | 2200 | 70.6 | 76.1 |
The physical property of table five, catalyst
| Catalyst | The C12-4 type | A | B |
| Breaking strength N/cm radially | 350．1 | 429．4 | 372．3 |
| The catalyst body sulfur content, PPm | 300 | 190 | 280 |
| Specific area m 2/g | 32．5 | 34．1 | 34．4 |
Claims (5)
1, a kind of high-temp transformation catalyst is characterized in that: by weight consist of iron oxide (Fe
2O
3) 100 parts, chrome green (Cr
2O
3) 2-9 part, potassium hydroxide (K
2The O meter) 0.3-0.6 part, auxiliary agent MO is cupric oxide 1.5-5 part, auxiliary agent M
1O is zinc oxide or aluminium oxide 0.5-4 part, and aluminium oxide (Al
2O
3) 0.3-1.1 part composition.
2, the preparation method of high temperature conversion catalyst according to claim 1 is characterized in that with ferrous nitrate solution, chromic acid solution, ammonium bicarbonate solution 3 material and flows homogeneous precipitation, and adds aluminum nitrate in N-process; Grinding material process secondary interpolation compounding agent solution, add semi-finished product, chromic acid solution, compounding agent solution, the potassium hydroxide that iron oxide is the master successively before driving stone roller, after rolling the each component mixing evenly then, through the granulation pneumatic conveying drying, calcination particle aftershaping promptly can be made into finished product.
3, the described preparation method of claim 2 when it is characterized in that grinding material, mixes to press after the auxiliary agent that secondary adds all once adds with the solution form and grinds.
4, the described preparation method of claim 2 is characterized in that catalyst size φ 6.0 ± 0.1 * 3.0 ± 0.1 (mm), is used for the radially high temperature shift type of furnace of low energy consumption synthesis ammonia factory axis.
5, the described preparation method of claim 2 is characterized in that adding compounding agent solution in the neutralization reaction process, with other three kinds of materials, forms four kinds of materials and stream and carries out neutralization-precipitation reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94113013A CN1065153C (en) | 1994-12-06 | 1994-12-06 | High-temperature shift catalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94113013A CN1065153C (en) | 1994-12-06 | 1994-12-06 | High-temperature shift catalyst and preparation method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN1124226A CN1124226A (en) | 1996-06-12 |
| CN1065153C true CN1065153C (en) | 2001-05-02 |
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ID=5036477
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| CN94113013A Expired - Fee Related CN1065153C (en) | 1994-12-06 | 1994-12-06 | High-temperature shift catalyst and preparation method thereof |
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| CN101491763B (en) * | 2008-12-24 | 2011-11-16 | 湖北双雄催化剂有限公司 | Preparation method capable of increasing sulfur tolerance of middle temperature iron-chromium shift catalyst using high-purity nano molybdenum trioxide |
| CN112547073B (en) * | 2020-12-14 | 2022-11-29 | 川化集团有限责任公司 | Copper-based hydrogenation catalyst, preparation method and application thereof |
| CN117943015A (en) * | 2022-10-27 | 2024-04-30 | 中国石油化工股份有限公司 | Preparation method and application of carbon monoxide isothermal shift catalyst |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0062410A1 (en) * | 1981-03-26 | 1982-10-13 | Imperial Chemical Industries Plc | Catalytic preparation of hydrogen from carbon monoxide and water |
| US4861745A (en) * | 1988-08-03 | 1989-08-29 | United Catalyst Inc. | High temperature shift catalyst and process for its manufacture |
| CN1045359A (en) * | 1990-03-17 | 1990-09-19 | 湖北省化学研究所 | The preparation method of iron-chromium-molybdenum system-carbonoxide transformation catalyst |
| CN1065815A (en) * | 1992-05-29 | 1992-11-04 | 天津大学 | The manufacture method of high-temp transformation catalyst |
-
1994
- 1994-12-06 CN CN94113013A patent/CN1065153C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0062410A1 (en) * | 1981-03-26 | 1982-10-13 | Imperial Chemical Industries Plc | Catalytic preparation of hydrogen from carbon monoxide and water |
| US4861745A (en) * | 1988-08-03 | 1989-08-29 | United Catalyst Inc. | High temperature shift catalyst and process for its manufacture |
| CN1045359A (en) * | 1990-03-17 | 1990-09-19 | 湖北省化学研究所 | The preparation method of iron-chromium-molybdenum system-carbonoxide transformation catalyst |
| CN1065815A (en) * | 1992-05-29 | 1992-11-04 | 天津大学 | The manufacture method of high-temp transformation catalyst |
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