CN1089634C - Method for preparing cobalt olybdenum catalyst with resistance of changed sulfur content and anti low sulfur content - Google Patents

Method for preparing cobalt olybdenum catalyst with resistance of changed sulfur content and anti low sulfur content Download PDF

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CN1089634C
CN1089634C CN99116562A CN99116562A CN1089634C CN 1089634 C CN1089634 C CN 1089634C CN 99116562 A CN99116562 A CN 99116562A CN 99116562 A CN99116562 A CN 99116562A CN 1089634 C CN1089634 C CN 1089634C
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acid
catalyst
cobalt
maceration extract
ammonium molybdate
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CN1242260A (en
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陈劲松
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Huashuo Technology Co., Ltd.
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HUBEI RESEARCH INSTITUTE OF CHEMISTRY
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Abstract

The present invention relates to a method for preparing an anti-low-sulphur cobalt-molybdenum sulphur-resisting transformation catalyst. The present invention is the improvement of the traditional impregnation method for preparing a cobalt-molybdenum CO sulphur-resisting transformation catalyst; the present invention comprises that an active gamma-Al2O3 carrier is impregnated with ammonium hydroxide solution prepared from soluble cobalt salt, ammonium molybdate and potassium carbonate, the impregnation solution is prepared from 4% of cobalt acetate, 10% of ammonium molybdate, 12.5% of potassium carbonate and 1% of ammonia, oxyacid potassium salt with an oxidation-reduction property is added in the impregnation solution, the oxyacid potassium salt accounts for 1% to 10% of the weight of the impregnation solution, the structure of molybdenum sulfide is changed, and dried cobalt-molybdenum sulphur-resisting transformation catalyst after impregnation has an anti-low-sulphur property.

Description

The preparation method of the co-mo antisulphuric transforming catalyst of anti-low-sulfur
The present invention relates to a kind of preparation method of cobalt molybdenum co surfer-resistant shift catalyst, particularly the preparation method of the co-mo antisulphuric transforming catalyst of anti-low-sulfur.
The Co-Mo sulfur-resistant transformation catalyst is since coming out, because its activity is good, and the operation wide temperature region, sulfur tolerance is strong, and is cheap, is widely used in the conversion section of synthesis ammonia plant.In recent years, U.S.3,850,840, U.S.3,957,962, U.S.4,153,580 and U.S.4,166,101 have reported with Al 2O 3Be the Co-Mo sulfur-resistant transformation catalyst of carrier, at present domestic and international co-mo antisulphuric transforming catalyst product of the same type mainly contains German BASF (BASF) K of company 8-11, the SSK of Denmark Top rope (TOPS φ e) company, the C of U.S. UCI company 25-02-1, the domestic national trade mark has the B301Q of Shanghai Chemical Research Inst, and the B302Q of Hubei Prov. Chemical Research Inst, B303Q also have the local product of some non-national trades mark, the SB302Q that produces as Chinese Shashi.Because Co-Mo is that the active constituent of transformation catalyst is Co-Mo sulfide, needs certain H in the semiwater gas 2S comes its sulfide component of balance, is hydrolysis otherwise can devulcanization take place under the effect of water vapour, thereby reduces its activity.Generally use reaction equation Calculate its balance H 2S concentration, because Thermodynamic Basis Data Source difference, its result of calculation differs greatly.Under existing conversion process condition, generally require the sulfide content of raw material coal gas to be higher than 0.25g/NM 3, and hydrogen sulfide content is 0.07g/NM in the semiwater gas of stipulating in the normal process index of Chinese the Ministry of Chemical Industry little nitrogen fertilizer industry promulgated by the ministries or commissions of the Central Government 3, add organic sulfur content 0.05-0.1g/NM 3, add up to 0.1-0.15g/NM 3, be lower than 0.25g/NM 3Level, therefore need improve hydrogen sulfide content in the semiwater gas artificially, certainly will require to change or strengthen the sulfur removal technology of traditional conversion gas, otherwise the activity of transformation catalyst reduces greatly because of desulfurication, the ordinary production difficulty is kept.For addressing this problem, the one, research low-sulfur low temperature shifting process is the co-mo antisulphuric transforming catalyst of the anti-low-sulfur of research again.Up to the present, still not deep enough comprehensively to the structure cognizing in cobalt-molybdenum series catalyst vulcanization mechanism and sulphided state structure, especially activated centre.Co-Mo sulfur-tolerant shift catalyst is not down to be CoS and the MoS of pure component in working order 2, because metal sulfide itself is very complicated, only two kinds of elements of cobalt molybdenum just have CoS, Co 9S 8, MoS 2, MoS 3, MoS 4Multiple sulfide, and its crystal structure of identical sulfide also is not quite similar, and often forms complicated sulphur and the non-stoichiometric compound of oxygen with auxiliary agent and carrier.Add the structure that different auxiliary agents changes its molybdenum sulfur compound and can improve anti-low-sulfur performance, US4,054,644 adds chlorine unit in cobaltmolybdate catalyst usually improves its anti-low-sulfur performance, but its processed complex, chlorine pollution is big, and effect is also not to the utmost desirable.Thereby need research add other processing simple, pollute little auxiliary agent and change the molybdenum sulfur compound structure, thereby improve its anti-low-sulfur performance, change or strengthen the sulfur removal technology of traditional conversion gas in order to avoid improve artificially hydrogen sulfide content in the semiwater gas.
The objective of the invention is Chinese patent 87107892,89108457,90102336.1 described co-mo antisulphuric transforming catalyst preparation methods are improved, a kind of preparation method of cobalt molybdenum co surfer-resistant shift catalyst of anti-low-sulfur is provided, it is the auxiliary agent that adds no chlorine pollution in the maceration extract of traditional immersion process for preparing catalyst, change the structure of sulfuration back molybdenum sulphide, make its performance, be applicable to that sulfide hydrogen is the conversion of the semiwater gas of amount usually with anti-low-sulfur.
The objective of the invention is to adopt following method to realize, as Chinese patent 87107892, with the active γ-Al of carrier 2O 3(be selected from cobalt nitrate with the solubility cobalt salt, cobalt chloride, cobalt acetate, a kind of in the cobaltous sulfate), the ammonia spirit that ammonium molybdate and potash form soaks altogether, the concentration of maceration extract is with the concentration described in the Chinese patent 87107892, such as cobalt acetate 4%, ammonium molybdate 10%, potash 12.5%, ammonia 1%, in maceration extract, add nitric acid or nitrous acid, sulfurous acid, thiosulfuric acid, wolframic acid, mangaic acid, chromic acid, sulfuric acid, acetic acid, a kind of soluble potassium salt of oxyacid in the oxalic acid, oxysalt concentration is counted 1%-10% (weight) with maceration extract, more preferably 3-5% floods post-drying and makes product.Product catalyst is formed identical with the patent No. 87108792, contains CoO3-7%, MoO 315-22%, K 2O5-20%.
Because the oxysalt that adds has certain oxidation-reduction quality, the oxygen sulphur ratio in the non-stoichiometric compound of the molybdenum that generates behind the catalyst vulcanization and sulphur and oxygen is changed, to change its active and anti-low-sulfur performance.
Embodiment 1:
With the active γ-Al of 60-80 purpose 2O 3Carrier soaks altogether with the ammonia spirit that cobalt acetate, ammonium molybdate, potash form, the concentration of each thing of maceration extract is with the concentration described in the application number 87107892, be cobalt acetate 4%, ammonium molybdate 10%, potash 12.5%, ammonia 1%, in maceration extract, add potassium nitrate to content 1% (weight), behind the dipping at 50-150 ℃ of dry No. 1 product.
Embodiment 2:
With the active γ-Al of 60-80 purpose 2O 3Carrier soaks altogether with the ammonia spirit that cobalt acetate and ammonium molybdate, potash form, the concentration of cobalt acetate, ammonium molybdate, potash, ammonia is with embodiment 1 in the maceration extract, in maceration extract, add potassium nitrate to content 2% (weight), behind the dipping at 50-150 ℃ of dry No. 2 products.
Embodiment 3,4,5:
With the active γ-Al of three parts of 60-80 purposes 2O 3Carrier soaks altogether with the ammonia spirit that three parts of cobalt acetates and ammonium molybdate, potash form respectively, the concentration of cobalt acetate, ammonium molybdate, potash, ammonia is with embodiment 1 in the maceration extract, in above-mentioned three portions of maceration extracts, add potassium nitrate content and be respectively 4%, 8%, 15% (weight), behind the dipping at 50-150 ℃ of dry 3,4, No. 5 products.
Embodiment 6:
With the active γ-Al of 60-80 purpose 2O 3Carrier soaks altogether with the ammonia spirit that cobalt acetate and ammonium molybdate, potash form, the concentration of cobalt acetate, ammonium molybdate, potash, ammonia is with embodiment 1 in the maceration extract, in maceration extract, add potassium nitrite to content 1% (weight), behind the dipping at 50-150 ℃ of dry No. 6 products.
Embodiment 7,8,9,10:
With the active γ-Al of four parts of 60-80 purposes 2O 3Carrier soaks altogether with the ammonia spirit that four parts of cobalt acetates and ammonium molybdate, potash form respectively, the concentration of cobalt acetate, ammonium molybdate, potash, ammonia is with embodiment 1 in the maceration extract, in above-mentioned four portions of maceration extracts, add potassium nitrite respectively to content be 2%, 4%, 8%, 15% (weight), behind the dipping at 50-150 ℃ of dry 7,8,9, No. 10 products.
Embodiment 11:
With the active γ-Al of 60-80 purpose 2O 3Carrier soaks altogether with the ammonia spirit that cobalt acetate and ammonium molybdate, potash form, the concentration of cobalt acetate, ammonium molybdate, potash, ammonia is with embodiment 1 in the maceration extract, in maceration extract, add potassium thiosulfate to content 1% (weight), behind the dipping at 50-150 ℃ of dry No. 11 products.
Embodiment 12,13,14,15:
With the active γ-Al of four parts of 60-80 purposes 2O 3Carrier soaks altogether with the ammonia spirit that four parts of cobalt acetates and ammonium molybdate, potash form respectively, the concentration of cobalt acetate, ammonium molybdate, potash, ammonia is with embodiment 1 in the maceration extract, in above-mentioned four portions of maceration extracts, add potassium thiosulfate respectively to content be 2%, 4%, 8%, 15% (weight), dry that product is respectively 12,13,14, No. 15 at 50-150 ℃ behind the dipping.
Embodiment 16:
With the active γ-Al of 60-80 purpose 2O 3Carrier soaks altogether with the ammonia spirit that cobalt acetate, ammonium molybdate, potash form, the concentration of each thing of maceration extract is with the concentration described in the application number 87107892, be cobalt acetate 4%, ammonium molybdate 10%, potash 12.5%, ammonia 1%, in maceration extract, add potassium chromate to content 1% (weight), behind the dipping at 50-150 ℃ of dry No. 16 products.
Embodiment 17,18,19,20:
With the active γ-Al of four parts of 60-80 purposes 2O 3Carrier soaks altogether with the ammonia spirit that four parts of cobalt acetates and ammonium molybdate, potash form respectively, the concentration of cobalt acetate, ammonium molybdate, potash, ammonia is with embodiment 1 in the maceration extract, in above-mentioned four portions of maceration extracts, add potassium chromate respectively to content be 2%, 4%, 8%, 15% (weight), behind the dipping after 50-150 ℃ of drying 12,13,14, No. 15 products.
Embodiment 21:
With the active γ-Al of 60-80 purpose 2O 3Carrier soaks altogether with the ammonia spirit that cobalt acetate and ammonium molybdate, potash form, the concentration of cobalt acetate, ammonium molybdate, potash, ammonia is with embodiment 1 in the maceration extract, in maceration extract, add potassium tungstate to content 1% (weight), after 50-150 ℃ of drying, get No. 21 products behind the dipping.
Embodiment 22,23,24:
With the active γ-Al of three parts of 60-80 purposes 2O 3Carrier soaks altogether with the ammonia spirit that three parts of cobalt acetates and ammonium molybdate, potash form respectively, the concentration of cobalt acetate, ammonium molybdate, potash, ammonia is with embodiment 1 in the maceration extract, in above-mentioned three portions of maceration extracts, add potassium tungstate to content and be respectively 2%, 4%, 6% (weight), after 50-150 ℃ of drying, get 22,23, No. 24 products behind the dipping.
Embodiment 25,26,27,28,29:
With the active γ-Al of five parts of 60-80 purposes 2O 3Carrier soaks altogether with the ammonia spirit that five parts of cobalt acetates and ammonium molybdate, potash form respectively, the concentration of cobalt acetate, ammonium molybdate, potash, ammonia is with embodiment 1 in the maceration extract, in above-mentioned five portions of maceration extracts, add respectively potassium sulfite 5%, potassium sulfate 5%, potassium manganate 5%, potassium acetate 5%, potassium oxalate 5% (all with the maceration extract weighing scale), after 50-150 ℃ of drying, get 25,26,27,28, No. 29 products behind the dipping.
Embodiment 30:
With the active γ-Al of 60-80 purpose 2O 3Carrier Co (HCOO) 2The ammonia spirit that forms with ammonium molybdate, potash soaks Co in the maceration extract (HCOO) altogether 23.5%, ammonium molybdate 10%, potash 12.5%, ammonia 1%, the sour potassium of the inferior pin of adding gets No. 30 products to content 10% (weight) after 50-150 ℃ of drying behind the dipping in maceration extract.
Prepared catalyst 1-4%H 2S or CS 2Adopt the sulfuration of Chinese patent 89100315 methods, perhaps use 1-4%CS 2Adopt the sulfuration of Chinese patent 91102838.2 methods.This test CS 2Sulfuration, catalyst temperature rise to 200 ℃ begin to add CS 2, concentration is with H 2S counts 15g/NM 3Semiwater gas, at 200-300 ℃ of following H 2S penetrated 1-6 hour, continued sulfuration then and be warming up to 375-500 ℃ gradually to vulcanize H 1-6 hour 2The S breakthrough concentration is greater than 10g/NM 3Promptly vulcanizate.
The catalyst activity test condition is to carry out in the testing arrangement of former granularity φ 3-5mm, and condition is: normal pressure, tube inner diameter 32mm, catalyst volume are 30ml, air speed 500h -1, steam-to-gas ratio 0.5, unstripped gas are semiwater gas, 190 ℃ of temperature, and activity is represented with the carbon monoxide conversion ratio.
The selection of devulcanization condition: being convenient to observe in order to improve the devulcanization reaction speed, is 25mg/NM with the total sulfur 3Semiwater gas, normal pressure, 400 ℃, steam-to-gas ratio 0.5 carried out devulcanization reaction 10 hours, immediately the cooling test activity.
Co-mo antisulphuric transforming catalyst embodiment 1-30 product with catalyst B 301Q of the same type, B302Q, SB302Q, B303Q and the anti-low-sulfur of the present invention of market supply, vulcanize together and test its shift activity of 190 ℃, carry out devulcanization reaction 12 hours then, be reduced to 190 ℃ of test its activity (representing) again with the CO interconversion rate.Owing to can lose the part low temperature active after catalyst at high temperature uses, in order to eliminate these errors, above-mentioned 28 kinds of catalyst were kept 12 hours down for 400 ℃ at dried semiwater gas, cool to 190 ℃ of test its activity (activity after heat-resisting) again, represent that with the CO interconversion rate it the results are shown in Table 1.
Applied at elevated temperature is slightly influential to its low temperature active as can be known from table, and interconversion rate descends about 1%, in the test error scope.It can be seen from the table, its anti-low-sulfur performance of various sulfur-resistant transformation catalysts is different.The anti-low-sulfur ability of catalyst of the present invention obviously is better than the catalyst of other model, and catalyst devulcanization deactivation phenomenom of the present invention descends significantly.It is good that the concentration that adds oxyacid sylvite in maceration extract is counted the anti-low-sulfur performance of catalyst that 1%-10% (weight) makes with maceration extract, the total cure hydrogen＞100mg/NM in the semiwater gas 3Get final product.The concentration that adds oxyacid sylvite in maceration extract is counted the anti-low-sulfur best performance of the catalyst that 3%-5% makes with maceration extract.
The devulcanization result of the test of the various como shift catalysts of anti-sulphur of table 1
Catalyst Former active % Active % after heat-resisting Active % after the devulcanization The active conservation rate % of devulcanization
B301Q 78.2 68.0 59.5 87.5
B302Q 79.5 78.2 62.6 80.1
SB302Q 42.7 41.5 27.8 67.0
B303Q 86.1 85.0 76.5 90.0
1 75.3 74.2 68.2 91.9
2 78.0 77.0 73.8 95.9
3 81.7 80.5 80.1 99.5
4 78.3 77.2 72.6 94.1
5 70.6 69.0 60.0 87.0
6 73.1 72.2 65.6 90.9
7 76.0 75.0 70.0 94.9
8 79.6 78.5 77.3 98.5
9 76.1 75.2 70.0 93.1
10 68.2 67.0 58.3 87.0
11 72.2 71.2 64.6 90.7
12 75.1 74.0 70.1 94.7
13 78.7 77.5 76.2 98.3
14 75.2 74.2 69.5 93.6
15 67.3 66.0 57.4 86.9
16 72.7 71.6 64.5 90.0
17 75.6 74.3 69.8 94.0
18 79.3 78.5 76.5 97.4
19 75.7 74.7 69.4 92.9
20 67.8 66.9 57.7 86.2
21 75.5 74.4 68.2 91.7
22 78.2 77.2 73.9 95.7
23 81.9 80.7 80.1 99.3
24 78.5 77.5 72.8 93.9
25 78.4 77.6 74.5 97.3
26 78.0 76.5 75.0 98.0
27 76.3 75.0 73.2 97.6
28 80.1 78.5 77.7 99.0
29 77.2 76.4 75.0 98.2
30 80.3 78.0 71.4 91.5

Claims (2)

1, a kind of preparation method of co-mo antisulphuric transforming catalyst of anti-low-sulfur, it is with the active γ-Al of carrier 2O 3The ammonia spirit that forms with solubility cobalt salt, ammonium molybdate, potash soaks altogether, the concentration of each thing of maceration extract is solubility cobalt salt 4%, ammonium molybdate 10%, potash 12.5%, ammonia 1%, dipping is rear 50-150 ℃ of drying, it is characterized in that having added in maceration extract and be selected from any soluble potassium salt in oxyacid nitric acid, nitrous acid, sulfurous acid, sulfuric acid, thiosulfuric acid, wolframic acid, acetic acid, the oxalic acid, its addition is the 1%-10% of maceration extract weight.
2, Preparation of catalysts method as claimed in claim 1, it is characterized in that having added in maceration extract and be selected from any soluble potassium salt in oxyacid nitric acid, nitrous acid, sulfurous acid, sulfuric acid, thiosulfuric acid, wolframic acid acetic acid, the oxalic acid, its addition is the 3%-5% of maceration extract weight.
CN99116562A 1999-07-23 1999-07-23 Method for preparing cobalt olybdenum catalyst with resistance of changed sulfur content and anti low sulfur content Expired - Lifetime CN1089634C (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108940297A (en) * 2017-05-29 2018-12-07 镇江瑞德新材料科技研发有限公司 A kind of novel processing step of co-mo antisulphuric transforming catalyst

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* Cited by examiner, † Cited by third party
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DE10207926A1 (en) 2002-02-23 2003-09-11 Clariant Gmbh Process for the preparation of primary amines by hydrogenation of nitriles
CN101760351B (en) * 2008-12-23 2010-12-15 李宝利 High efficiency molybdate ammonium cobalt complex tower-cleaning agent and preparation method thereof
CN102423623B (en) * 2011-08-29 2013-07-10 华烁科技股份有限公司 Multifunctional raw gas purifying agent, preparation method and application method thereof
CN115646529B (en) * 2022-10-31 2024-03-12 湖北禾谷环保有限公司 Pre-sulfurized CO sulfur-tolerant shift catalyst and preparation method and application thereof

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US3850841A (en) * 1969-11-10 1974-11-26 Exxon Research Engineering Co Shift process for new catalyst
CN1042482A (en) * 1989-11-07 1990-05-30 湖北省化学研究所 The preparation method of cobalt-molybdenum-carbonoxide transformation catalyst
CN1022543C (en) * 1990-04-21 1993-10-27 湖北省化学研究所 Process to prepare Co-Mo catalyst for CO transformation

Patent Citations (3)

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US3850841A (en) * 1969-11-10 1974-11-26 Exxon Research Engineering Co Shift process for new catalyst
CN1042482A (en) * 1989-11-07 1990-05-30 湖北省化学研究所 The preparation method of cobalt-molybdenum-carbonoxide transformation catalyst
CN1022543C (en) * 1990-04-21 1993-10-27 湖北省化学研究所 Process to prepare Co-Mo catalyst for CO transformation

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108940297A (en) * 2017-05-29 2018-12-07 镇江瑞德新材料科技研发有限公司 A kind of novel processing step of co-mo antisulphuric transforming catalyst

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