CN1189394A - Normal atmospheric temp. and low temp. organic sulphur hydrolyst and its prepn. - Google Patents

Normal atmospheric temp. and low temp. organic sulphur hydrolyst and its prepn. Download PDF

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Publication number
CN1189394A
CN1189394A CN97125340A CN97125340A CN1189394A CN 1189394 A CN1189394 A CN 1189394A CN 97125340 A CN97125340 A CN 97125340A CN 97125340 A CN97125340 A CN 97125340A CN 1189394 A CN1189394 A CN 1189394A
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carrier
temp
aqueous solution
hydrolyst
catalyst
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CN97125340A
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CN1080584C (en
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李春虎
上官炬
李彦旭
樊惠玲
郭汉贤
郭晓汾
郭红生
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Taiyuan University of Technology
Taiyuan University of Science and Technology
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Taiyuan University of Technology
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Abstract

An ordinary (or low)-temp. hydrolytic catalyst for organosulfur contains (NH4)6Mo7O24.4H2O, K2CO3 and low-density spherical gamma-Al2O3 carrier and is prepared isovolume impregnating of the aqueous solution of (NH4)6Mo7O24.4H2O to spherical gamma-Al2O3 carrier, drying, calcine activation, impregnation of the aqueous solution of K2CO3, drying and calcine. Its advantages include stong hydrolytic catalysis action to COS and CS2, long service life and a certain power to resist oxygen poisoning. The hydrolytic conversion rate at 0-100 deg.C can reach more than 98%. It is suitable to remove organosulfur from raw gas in synthesis, chemical, petroleum and natural gas industries.

Description

Normal low temperature organic sulfur hydrolyst and preparation
Normal low temperature organic sulfur hydrolyst of the present invention and preparation method belong to the Preparation of Catalyst field, and specifically relating to a kind of is the method for the desulfurizing decontaminating agent of feedstock production material gas with coal, oil and natural gas.
Be the material gas of feedstock production with coal, oil and natural gas at present, after wet desulphurization, still have 3-50mgS/m 3Organic sulfur exists, and is wherein most of with COS and CS 2Form exists, and COS and CS 2Mol ratio is about 9: 1.This part organic sulfur is with conventional absorption process such as iron oxide process, zinc oxide method and activated carbon method, is difficult to remove or uneconomical worthwhile.These organic sulfurs are not directly brought follow-up workshop section into if do not remove, to cause catalyst poisoning, technological process worsens, copper base connection alcohol catalyst and the iron-based synthetic ammonia catalyst used as the many middle small fertilizer plant of China, service life, less than was 1 year, traced it to its cause, and mostly was organic sulfur removal and not exclusively caused due to the sulfur poisoning, but also easily causing concise workshop cuprammonium washing tower for removing CO to stop up, copper loss is crossed high adverse consequences.COS and CS 2Available catalyzing hydrolysis is removed.The clear 61-259755 of Japan Patent passes through at Al 2O 3Last interpolation barium salt, the method 600 ℃ of roastings has prepared the COS hydrolyst then, and it then is at Al that clear 63-224736 prepares the COS hydrolyst 2O 3Last interpolation KOH or NaOH, the catalyst of being invented can only be higher than use on 100 ℃.As for CS 2Hydrolysis generally needs more than 200 ℃.The patent CN1069673A (application number 92104524.7) that domestic Hubei chemistry is invented then is at Al 2O 3Last load K 2CO 3Hydrolysis temperature is a room temperature to 50 ℃.All these catalyst have following shortcoming: 1. because active constituent is single, and sylvite, sodium salt and barium salt etc. are all soluble in water, active constituent in use easily take place run off, thus the lost of life.2. when having micro amount of oxygen to exist in the gas, oxygen poisoning more easily takes place in hydrolysing activity more height, thereby reduces activity, influences result of use.
Normal low temperature organic sulfur hydrolyst of the present invention and preparation purpose are to overcome effectively the defective that above-mentioned Preparation of Catalyst exists, thereby a kind of have active high, activity stabilized, antioxygen poisoning and normal low temperature organic sulfur hydrolyst of the simple dual-active of preparation method and preparation method are provided.
The present invention realizes by following method, with γ-Al 2O 3For its physical and chemical performance of carrier is shown in Table 1.
Table 1 γ-Al 2O 3Physicochemical properties appearance size bulk density specific area water absorption rate mechanical strength pore volume
Mm g/ml m 2/ g ml/g newton/ml/g white spheroid φ 3-5 0.65-0.85 200-350 0.35-0.70 〉=30～0.50
The normal low temperature organic sulfur hydrolyst of the present invention, by the compound that contains molybdenum and potassium as active constituent, γ-Al 2O 3Forming for carrier, it is characterized in that the dual-active component, is (the NH that contains vehicle weight 0.5-8% 4) 6Mo 7O 244H 2O and 3-10%K 2CO 3, carrier is selected low-density spherical gamma-Al for use 2O 3, and need satisfy following requirement:
Spherical diameter: 3-5mm
Water absorption rate: 0.35-0.70ml/g
Specific area: 200-350m 2/ g
Mechanical strength: 〉=30 newton/
The present invention prepares the method for catalyst, and its characteristics are to adopt equi-volume impregnating, and this method is to be selected from spherical γ-Al 2O 3Carrier is with (NH 4) 6Mo 7O 244H 2O aqueous solution incipient impregnation is used K again after 50～120 ℃ of dryings and 350～480 ℃ of roastings 2CO 3Aqueous solution incipient impregnation, (NH on carrier 4) 6Mo 7O 244H 2O and K 2CO 3After amount reaches requirement, make through 50～120 ℃ of dryings and 350～480 ℃ of calcination activations again.
Preparation process of the present invention is as follows: at first with the (NH of variable concentrations 4) 6Mo 7O 244H 2The O aqueous solution is impregnated into spherical gamma-Al with equi-volume impregnating 2O 3On the carrier, in 50～120 ℃ of following dry 4h,, flood certain density K with equi-volume impregnating again behind the placement 24h then at 350 ℃ of following calcination activation 3h 2CO 3The aqueous solution, afterwards at 50-120 ℃ of following dry 4h, 350～480 times roasting 3h and making.The catalyst activity property testing carries out in the fixed bed glass reactor, 26 millimeters of reactor inside diameter, 100 millimeters of isothermal region height, 10 milliliters of loaded catalysts, the sphere that particle diameter is 3～5 millimeters, air speed 2000h -1, normal pressure, water/vapour 〉=200,50 ℃ of reaction temperatures, unstripped gas is a syngas for synthetic ammonia, activity is represented with the COS hydrolysis conversion.
Catalyst of the present invention is used for synthetic ammonia, synthesizing methanol, low-carbon alcohols, the synthetic wet goods C of F-T 1The smart desulfurization of chemistry and other material gas.Its active high, activity stabilized, antioxygen poisoning, preparation method simply especially utilize equi-volume impregnating not have significant loss and three waste discharge, hydrolysis conversion height.
With subordinate list, comparative example and embodiment describe the present invention in detail below.
Embodiment:
Difference weighing γ-Al 2O 3100g * 5 part are put into flask at the bottom of the garden of 6 500ml respectively.Take by weighing (the NH of 0.5g, 2g, 4g, 6g, 8g respectively 4) 6Mo 7O 244H 2O is dissolved in water 50 milliliters, takes by weighing 4gK 2CO 3Be dissolved in water in 50 ml solns.(NH with 5 kinds of variable concentrations 4) 6Mo 7O 244H 2O is added drop-wise to γ-Al respectively 2O 3Last incipient impregnation is placed 24h, then at 100 ℃ of dry 4h, floods K more respectively behind 350 ℃ of following calcination activation 3h 2CO 3Solution is placed 4h 120 ℃ of following dry 4h then, and 350 ℃ of following calcination activation 3h are all contained 4%K 2CO 3And contain 0.5%, 2%, 4%, 6% and 8% (NH 4) 6Mo 7O 244H 2γ-Al of O 2O 35 kinds of catalyst of base.Its activity data sees Table 2.
Table 2 different activities component addition influences catalyst (NH to the hydrolyzation catalysis activity 4) 6Mo 7O 244H 2O addition/%K 2CO 3Addition/% COS conversion ratio/% 1 #0.5 4 75.8 2 #24 98.5 3 #44 81.0 4 #64 71.3 5 #84 65.4 operating conditions: temperature: 50 ℃, air speed: 2000h -1, H 2O/COS 〉=200
As seen, load 4%K 2CO 3With 2% (NH 4) 6Mo 7O 244H 2Hydrolysis has best hydrolysing activity to the catalyst of O to COS.
Comparison example:
According to 2 #The prescription of catalyst, expansion equipment and output, and to name this catalyst be the TGH-4 type and compare experiment with the TGH-2Q and the EH-1Q catalyst of present domestic use, the results are shown in Table shown in 3.
The following three kinds of catalyst activity C.Ts of table 3 different temperatures (℃) 30 40 45 50EH-1Q, 32.9 77.6 85.5 94.6TGH-2Q, 26.7 60.0 81.4 93.2TGH-4,54.7 90.9 99.1 100 operating conditions: import COSConcentration: 60mg/m 3, air speed: 2000h -1, H 2The visible TGH-4 type catalyst in O/COS 〉=200 used one-component hydrolyst on the market.Embodiment:
TGH-4 type hydrolyst is used for CS 2Hydrolysis catalysis reaction the results are shown in Table 4.
The synthermal CS down of table 4 2The hydrolysing activity temperature (℃) 60 80 100 120 140 conversion ratios (%), 25.1 58.3 80.9 85.8 98.6 operating conditions: air speed: 2000h -1, H 2O/CS 2〉=200
As seen this catalyst is to CS 2Quite high hydrolysing activity is also arranged under higher temperature.
Embodiment:
TGH-4 type catalyst is used for the smart desulfurization of synthetic ammonia feedstock after certain chemical fertilizer factory's carbonization.Reactor diameter φ 2200mm, loadings 5m 3, operating pressure 0.5MPa, 50 ℃ of temperature, air speed 1500h -1, import COS concentration 0.2～5mgS/m 3, moving inactivation did not still take place after 18 months, its operation result sees Table 5.
TGH-4 type catalyst operation result is used in table 5 industry
Hydrolysis reactor hydrolysis reactor running time/sky import COS concentration outlet COS concentration conversion ratio % mgS/m 3MgS/m 3
1 0.42 0 100
30 0.9 0 100
60 1.8 0 100
90 3.2 0 100
120 2.5 0 100
150 2.3 0 100
180 2.8 0 100
400 1.8 0 100

Claims (2)

1. normal low temperature organic sulfur hydrolyst, by the compound that contains molybdenum and potassium as active constituent, γ-Al 2O 3Forming for carrier, it is characterized in that the dual-active component, is (the NH that contains vehicle weight 0.5-8% 4) 6Mo 7O 244H 2O and 3-10%K 2CO 3, carrier is selected low-density spherical gamma-Al for use 2O 3, and need satisfy following requirement:
Spherical diameter: 3-5mm
Water absorption rate: 0.35-0.70ml/g
Specific area: 200-350m 2/ g
Mechanical strength: 〉=30 newton/
2. method for preparing the described catalyst of claim 1, its characteristics are to adopt equi-volume impregnating, and this method is to be selected from spherical γ-Al 2O 3Carrier is with (NH 4) 6Mo 7O 244H 2O aqueous solution incipient impregnation is used K again after 50～120 ℃ of dryings and 350～480 ℃ of roastings 2CO 3Aqueous solution incipient impregnation, (NH on carrier 4) 6Mo 7O 244H 2O and K 2CO 3After amount reaches requirement, make through 50～120 ℃ of dryings and 350～480 ℃ of calcination activations again.
CN97125340A 1997-12-26 1997-12-26 Normal atmospheric temp. and low temp. organic sulphur hydrolyst and its prepn. Expired - Fee Related CN1080584C (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100345629C (en) * 2003-10-10 2007-10-31 德古萨股份公司 Catalyst for synthesizing methane thiol from synthetic gas containing high-concentration hydrogen sulfide
CN100431668C (en) * 2004-05-28 2008-11-12 长春东狮科贸实业有限公司 Hydrolyst for COS and CS2 and application thereof
CN102408923A (en) * 2011-10-11 2012-04-11 华烁科技股份有限公司 Hydrolysis method of COS in synthesis gas based on high-density circulating fluidization and gasification process
CN111252766A (en) * 2020-01-20 2020-06-09 华东能源环保股份有限公司 High-efficiency desulfurization process for carbon dioxide feed gas
CN113145104A (en) * 2021-04-21 2021-07-23 山西普丽环境工程股份有限公司 Preparation method of hydrolysis desulfurization catalyst
CN114471518A (en) * 2020-10-23 2022-05-13 中国石油化工股份有限公司 Normal-temperature COS (COS) hydrolyzing agent as well as preparation method and application thereof
CN115106108B (en) * 2021-03-18 2023-11-14 宝山钢铁股份有限公司 COS hydrolysis catalyst for blast furnace gas and preparation method thereof

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2608458B1 (en) * 1986-12-23 1989-03-10 Rhone Poulenc Chimie CATALYST BASED ON CERIUM OXIDE AND METHOD FOR THE TREATMENT OF INDUSTRIAL GASES CONTAINING SULFUR COMPOUNDS
JPS63224736A (en) * 1987-03-13 1988-09-19 Jgc Corp Catalyst for hydrolizing carbonyl sulfide
JPH047020A (en) * 1990-04-23 1992-01-10 Kawasaki Steel Corp Removal of organic sulfur compound from gas
CN1029594C (en) * 1992-06-08 1995-08-30 湖北省化学研究所 Normal tempreture organic sulphur hydrolysis catalyst and its preparation
CN1056096C (en) * 1994-02-21 2000-09-06 中国石化齐鲁石油化工公司 Sulfur carbonyl hydrolytic catalyzer
CN1048916C (en) * 1995-08-16 2000-02-02 南京化学工业(集团)公司催化剂厂 Organic sulfur hydrolyst and its preparation

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100345629C (en) * 2003-10-10 2007-10-31 德古萨股份公司 Catalyst for synthesizing methane thiol from synthetic gas containing high-concentration hydrogen sulfide
CN100431668C (en) * 2004-05-28 2008-11-12 长春东狮科贸实业有限公司 Hydrolyst for COS and CS2 and application thereof
CN102408923A (en) * 2011-10-11 2012-04-11 华烁科技股份有限公司 Hydrolysis method of COS in synthesis gas based on high-density circulating fluidization and gasification process
CN102408923B (en) * 2011-10-11 2013-07-17 华烁科技股份有限公司 Hydrolysis method of COS in synthesis gas based on high-density circulating fluidization and gasification process
CN111252766A (en) * 2020-01-20 2020-06-09 华东能源环保股份有限公司 High-efficiency desulfurization process for carbon dioxide feed gas
CN114471518A (en) * 2020-10-23 2022-05-13 中国石油化工股份有限公司 Normal-temperature COS (COS) hydrolyzing agent as well as preparation method and application thereof
CN114471518B (en) * 2020-10-23 2024-01-09 中国石油化工股份有限公司 Normal-temperature COS (COS) hydrolyzer as well as preparation method and application thereof
CN115106108B (en) * 2021-03-18 2023-11-14 宝山钢铁股份有限公司 COS hydrolysis catalyst for blast furnace gas and preparation method thereof
CN113145104A (en) * 2021-04-21 2021-07-23 山西普丽环境工程股份有限公司 Preparation method of hydrolysis desulfurization catalyst

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