CN1102420C

CN1102420C - Hydrolytic catalyst of carbonyl sulfur and its preparing process and application

Info

Publication number: CN1102420C
Application number: CN00119385A
Authority: CN
Inventors: 朱玉雷; 苏化连; 相宏伟; 徐元源; 李永旺
Original assignee: Shanxi Institute of Coal Chemistry of CAS
Current assignee: Shanxi Institute of Coal Chemistry of CAS
Priority date: 2000-07-11
Filing date: 2000-07-11
Publication date: 2003-03-05
Anticipated expiration: 2020-07-11
Also published as: CN1304781A

Abstract

一种羰基硫水解催化剂，其组成为γ-Al₂O₃ 83-97%，K₂O2-15%，BaO 0.1-2%。该催化剂是采用等体积溶液浸渍法进行制备，其用途是在温度80-150℃，常压，COS含量小于800mg/m³，空速6000-9000h^-1条件下进行脱硫。本发明具有高活性，高空速，COS转化率大于95%的优点。A carbonyl sulfide hydrolysis catalyst, the composition of which is γ-Al ₂ O ₃ 83-97%, K ₂ O2-15%, BaO 0.1-2%. The catalyst is prepared by equal-volume solution impregnation method, and its purpose is to desulfurize under the conditions of temperature 80-150°C, normal pressure, COS content less than 800mg/m ³ , and space velocity 6000-9000h ^-1 . The invention has the advantages of high activity, high space velocity and COS conversion rate greater than 95%.

Description

A kind of hydrolytic catalyst of carbonyl sulfur and its production and use

The invention belongs to a kind of desulphurization catalyst, relate in particular to a kind of hydrolytic catalyst of carbonyl sulfur and its production and use.

In coal system synthetic raw gas, contain with H simultaneously ₂S is a main inorganic sulfur and based on the organic sulfur of COS.Sulfide is to Cu-series catalyst for synthesizing methanol, and copper is low change catalyzer, and nickel is methanation catalyst, and the murder by poisoning of F-T artificial oil ferrum-based catalyst is serious, and it can't normally be moved.In this class work, need it is removed.The technology that the removes comparative maturity of inorganic sulfur, and organic sulfur COS removes and also has many weak points.Cos catalyzing hydrolysis process is as follows: under low temperature, normal pressure and hydrolyst effect, COS is converted into inorganic sulphide H ₂S removes H with conventional desulfurizing agent then ₂S and reach the purpose that removes COS.

Chinese patent CN1069673 discloses a kind of COS hydrolyst, and it is at γ-Al ₂O ₃On the bead carrier, the K of dipping 2-25% ₂CO ₃, final products are made in the drying roasting.At 50 ℃, COS concentration 5mg/m ³, air speed 2000h ^-1Under the condition, the COS conversion ratio is greater than 95%, and this catalyst weak point is that processing unstripped gas COS content and air speed are lower.

Chinese patent CN1134312 has announced a kind of organic desulfurizing agent.This catalyst is by γ-Al ₂O ₃And titanium dioxide (4-20%) composition, its preparation method is that refining aluminium oxide and titanium hydroxide are mixed the back roller forming in proportion.Carrying out washing treatment semi-finished product ball, activated again, the calcining product catalyst.At air speed 1800h ^-1, sulfur content 5000mg/m ³Under the condition, hydrolysis transforms.This catalyst weak point is that the unstripped gas air speed is lower.

The purpose of this invention is to provide a kind of big hydrolytic catalyst of carbonyl sulfur of unstripped gas air speed and its production and use of handling.

The each component percentage by weight of catalyst of the present invention is:

γ-Al ₂O ₃ 83-97％

K ₂O 2-15％

BaO 0.1-2％

Catalyst of the present invention adopts profit method preparation just, and concrete steps are as follows:

(1) gets γ-Al ₂O ₃Its total hole volume of sample determination

With commercially available γ-Al ₂O ₃Sample is heated to 200 ℃, and cooling takes by weighing 100g in the air of drying then, then sample is dipped in the water, and no bubble is overflowed on sample, with filter paper the water of sample surfaces is removed, and claims the weightening finish value of sample, calculates the volume of water outlet, promptly gets porosity;

(2) form by catalyst and porosimeter is calculated the volume of required water, K ₂O and BaO predecessor KOH and Ba (OH) ₂Soluble in water, wiring solution-forming adds γ-Al fully to solution ₂O ₃,, 300 ℃ of roastings 12 hours, obtain catalyst at last then 110 ℃ of dryings.

Catalyst of the present invention is used for COS hydrolysis organic sulfide removal, is that catalyst is contained in the fixed bed reactors, at temperature 80-150 ℃, and normal pressure, COS content is less than 800mg/m ³, air speed 6000-9000h ^-1Under the condition, the COS conversion ratio is greater than 95%.

Catalyst of the present invention compared with prior art has following advantage:

Catalyst has high activity, makes it have the adaptation high activity, makes it have the high-speed of adaptation 6000-9000h ^-1With high COS content 500-800mg/m ³Ability.

Embodiments of the invention are as follows:

Embodiment 1

(1) selecting specific area is 160m ²/ g, pore volume is commercially available γ-Al of 0.65 ₂O ₃

(2) get γ-Al ₂O ₃Its total hole volume of sample determination

With γ-Al ₂O ₃Sample is heated to 200 ℃, and cooling takes by weighing 100g in the air of drying then, then sample is dipped in the water, no bubble is overflowed on sample, with filter paper the water of sample surfaces is removed, claim that the weightening finish value of sample is 65g, the volume that gets water outlet is 65ml, promptly gets porosity 0.65ml/g;

(3) take by weighing Al ₂O ₃90g, KOH 10.1g, Ba (OH) ₂8H ₂O 3.1g, calculating institute's water requirement is 90g * 0.65ml/g=59ml, with KOH and Ba (OH) ₂8H ₂O is dissolved in the 59ml water, and wiring solution-forming adds γ-Al fully to solution ₂O ₃,, 300 ℃ of roastings 12 hours, obtain catalyst at last then 110 ℃ of dryings;

(4) catalyst is contained in fixed bed reactors (in the Φ 6 * 250mm), at 90 ℃ of temperature, normal pressure, air speed 8000h ^-1, COS content 700mg/m ³Condition under, the COS conversion ratio is 96.5%.

Embodiment 2

Take by weighing Al ₂O ₃95g, KOH 5.4g, Ba (OH) ₂8H ₂O 1.0g calculates institute's water requirement and equals 95g * 0.65ml/g=62ml, with KOH and Ba (OH) ₂8H ₂O is dissolved in the 62ml water, and wiring solution-forming adds γ-Al fully to solution ₂O ₃,, 300 ℃ of roastings 12 hours, obtain catalyst at last then 110 ℃ of dryings; Catalyst is contained in fixed bed reactors (in the Φ 6 * 250mm), at 110 ℃ of temperature, normal pressure, air speed 7000h ^-1, COS content 500mg/m ³Condition under, the COS conversion ratio is 96%.All the other are with embodiment 1.

Embodiment 3

Take by weighing Al ₂O ₃87.7g, KOH 14.3g, Ba (OH) ₂8H ₂O 0.6g calculates institute's water requirement and equals 87.7g * 0.65ml/g=57ml, with KOH and Ba (OH) ₂8H ₂O is dissolved in the 57ml water, and wiring solution-forming adds γ-Al fully to solution ₂O ₃,, 300 ℃ of roastings 12 hours, obtain catalyst at last then 110 ℃ of dryings; Catalyst is contained in fixed bed reactors (in the Φ 6 * 250mm), at 130 ℃ of temperature, normal pressure, air speed 6000h ^-1, COS content 650mg/m ³Condition under, the COS conversion ratio is 95.5%.All the other are with embodiment 1.

Embodiment 4

Take by weighing Al ₂O ₃84g, KOH 17.6g, Ba (OH) ₂8H ₂O 2.5g calculates institute's water requirement and equals 84g * 0.65ml/g=55ml, with KOH and Ba (OH) ₂8H ₂O is dissolved in the 55ml water, and wiring solution-forming adds γ-Al fully to solution ₂O ₃,, 300 ℃ of roastings 12 hours, obtain catalyst at last then 110 ℃ of dryings; Catalyst is contained in fixed bed reactors (in the Φ 6 * 250mm), at 130 ℃ of temperature, normal pressure, air speed 6500h ^-1, COS content 650mg/m ³Condition under, the COS conversion ratio is 95%.All the other are with embodiment 1.

Claims

1. a carbonyl sulfide hydrolysis catalyst is characterized in that the weight percent of each component of the catalyst is:

γ-Al ₂ O ₃ 83-97%

K ₂ O 2-15%

BaO 0.1-2%.

2. the preparation method of a kind of carbonyl sulfide hydrolysis catalyst as claimed in claim 1, is characterized in that:

(1) Take γ-Al ₂ O ₃ sample to measure its total pore volume

Heat the commercially available γ-Al ₂ O ₃ sample to 200°C, then cool it, weigh 100g in dry air, and then immerse the sample in water until no air bubbles escape from the sample, and remove the water on the surface of the sample with filter paper Remove, weigh the weight gain of the sample, calculate the volume of water, and get the porosity;

(2) Calculate the volume of water required according to the catalyst composition and porosity, dissolve KOH and Ba(OH) ₂ , the precursors of K ₂ O and BaO, in water to make a solution, and add the solution completely to γ-Al ₂ O ₃ , and then dried at 110°C, and finally calcined at 300°C for 12 hours to obtain a catalyst.

3. The application method of a carbonyl sulfide hydrolysis catalyst as claimed in claim 1, characterized in that the catalyst is installed in a fixed-bed reactor, at a temperature of 80-150°C, at normal pressure, with a COS content of less than 800mg/m ³ , in an empty Desulfurization is carried out under the condition of speed 6000-9000h ^-1 .