CN1095309A

CN1095309A - Novel hydrolytic catalyst of carbonyl sulfur

Info

Publication number: CN1095309A
Application number: CN94110471A
Authority: CN
Inventors: 房德仁; 尹长学; 李海洋; 周广林; 张文明
Original assignee: INST OF QILU PETRO-CHEMICAL Co; Qilu Petrochemical Co of Sinopec
Current assignee: INST OF QILU PETRO-CHEMICAL Co; Qilu Petrochemical Co of Sinopec
Priority date: 1994-02-21
Filing date: 1994-02-21
Publication date: 1994-11-23
Anticipated expiration: 2014-02-21
Also published as: CN1056096C

Abstract

In a kind of petrochemical process, particularly used normal temperature cos (COS) hydrolyst and preparation method in methyl alcohol, synthesis gas, the propylene industry consists of γ-Al ₂O ₃98.5～55% (m/m), TiO ₂1～20% (m/m), KOH0.5～25% (m/m) has extra high low temperature active, can reach the conversion ratio more than 98% in the time of 50 ℃, and activity stability and life-span are all high especially.

Description

Novel hydrolytic catalyst of carbonyl sulfur

The invention belongs to a kind of hydrolytic catalyst of carbonyl sulfur and preparation method in the petrochemical industry, is a kind of normal temperature hydrolytic catalyst of carbonyl sulfur.

Background of invention:

It in the industry such as synthetic ammonia, methyl alcohol is in the synthesis gas of raw material gas making with coal, coke, heavy oil that cos (COS) extensively is present in, and also is present in simultaneously in the hydrocarbon raw material such as propylene.Its existence has caused murder by poisoning to the downstream catalyst in the production process as methanol synthesis catalyst, polypropylene catalyst etc., has influenced the serviceability of downstream catalyst, for this reason, has developed the method for the multiple COS of removing.What wherein have practical value most is COS constant temperature catalyzing technology for hydrolyzing, and it is at normal temperatures, under the effect of hydrolyst, earlier COS is converted into the inorganic sulphide H that removes easily ₂S, and then remove H with conventional desulfurizing agent ₂S, thus reach the purpose of organic sulfide removal COS.

U.S. Pat, P4.444.987 and US, P4,455,446 disclose the catalyst that a kind of activated alumina is uploaded platinum sulfide, and the shortcoming of this catalyst is the cost height of catalyst, and needs regular regeneration, and general factory seldom uses.

U.S. Pat, P3.265,757 disclose a kind of normal temperature COS hydrolyst, and this catalyst is to be uploaded 0.5%～3.0% Na by activated alumina ₂O or K ₂The Japan Patent JP that O forms, 63,224,736 disclose a kind of catalyst, and it is the Na that uploads 1%-115% at activated alumina ₂O or K ₂O, and baking temperature prepares under 110～130 ℃ of conditions, and serviceability temperature is more than 100 ℃.

U.S. Pat .P4,491,516 and 0,195 534 of European patent EP invented a kind of activated alumina of any auxiliary agent that do not add as the COS hydrolyst.

Chinese patent CN1069673 discloses a kind of normal tempreture organic sulphur hydrolysis catalyst, and it is at γ-AL ₂O ₃Ball is uploaded 2%～25% K ₂CO ₃, form through＜120 ℃ of dryings.℃ COS content 1～5mg/m in room temperature～50 ³, air speed 2000h ^-1Under the condition, the COS hydrolysis conversion) 95%.

The advantage that all these activated aluminas or activated alumina are uploaded alkali metal hydroxide and alkali carbonate is that cost is low, the shortcoming of pure activated alumina catalyst is that low temperature active is poor, and the shortcoming of carrying the alkali metal activated alumina catalyst is that activity stability is poor, easily inactivation.And above-mentioned catalyst only is applicable to low COS unstripped gas, and general COS content is at 1～10ppm, and to the raw material of high COS content, activity of conversion is lower.

Purpose of the present invention, just be further to improve the low temperature active of COS hydrolyst, increase activity of such catalysts stability, simultaneously, widen the scope of intending desulfurization (COS) unstripped gas, and the life-span is long, is applicable to the raw material of different COS content, in particular for the COS hydrolyst of the raw material that removes high COS content.

The invention narration:

On the basis of having furtherd investigate normal temperature COS hydrolytic process, we think that the reason of catalyst activity decay mainly is because due to the surperficial sulfation, carrier is carried out modification can obviously prolong activity of such catalysts by adding suitable transition metal oxide, suppress the sulfation process, used TiO among the present invention ₂, ZrO ₂As modifier, reached its intended purposes Deng material, do not had in this former normal temperature COS hydrolyst.In addition, improve the conversion capability of catalyst to high-load COS, we think that key is that catalyst will have suitable pore passage structure, are beneficial to the transmitting effect of COS, and we have used special gelatinizing agent in the present invention, have reached this purpose.The present invention has determined the type and the content of active component also by test.

Specifically, the present invention is made up of preparing carriers, activity component impregnation and post processing three parts.

Carrier is made up of boehmite, modifier, pore creating material and gelatinizing agent four parts.By common practices through extrusion, drying, roasting and make.Alumina content is 80%～99% in the finished product carrier; Said modifier is TiO ₂, ZrO ₂Deng, TiO preferably ₂, its consumption accounts for 1%～20% of finished product carrier.

Said inorganic acid is a nitric acid, organic acid such as formic acid, acetate, oxalic acid, citric acid etc., preferably inorganic acid and organic acid mixture be as gelatinizing agent, and the citric acid preferably of the organic acid in the nitration mixture, its consumption be raw material form 0.5%～15%.

The baking temperature of carrier is 100～150 ℃, and sintering temperature is 500～700 ℃

Active component of the present invention is KOH or NaOH, and its consumption accounts for 0.5%～25% of whole catalyst, adopts solution dipping method to be downloaded on the above-mentioned carrier.Preferably select for use KOH as active component, the optimum amount scope is 5%～20%.

The 3rd step of Preparation of Catalyst is post processing, and is promptly dry, is lower than at baking temperature under 100 ℃ the condition, dryly promptly gets catalyst of the present invention more than 10 hours.

The composition of catalyst of the present invention is: AL ₂O ₃98.5%～55%(m/m)

TiO ₂0.1%～20%（m/m）

KOH 0.5%～25%（m/m）

The effect of invention:

Made up by above three parts, we have prepared all good COS ordinary-temp hydrolysis catalyst of a kind of low temperature active, activity stability, and this catalyst has the better conversion activity to high COS raw material, are a kind of novel COS ordinary-temp hydrolysis catalyst.This catalyst compares with the catalyst EH-1Q that the catalyst P 2312 for preparing by patent 3,265,757 reaches by patent CN1069673A preparation, and the result is as follows.

Air speed influence test

Get P2312, EH-1Q and each 0.5ml of catalyst of the present invention, granularity 40～60 orders, the internal diameter of packing into are in the glass reactor of Φ 4mm, use COS/H ₂Do reaction medium, behind the water saturation device, water content about 2% is analyzed 50 ℃ of reaction temperatures with the WLSP852 trace sulfur analyzer to COS content in the gas before and after the reaction.Result such as table one expression.

As seen, under all air speeds, the conversion ratio of catalyst of the present invention all is higher than the conversion ratio of P2312 and EH-IQ.

The temperature effect test:

Test method is the same, fixation reaction gas space velocity 5000h ^-1The result as shown in Table 2.

By table two as seen, under each temperature, the COS conversion ratio of catalyst of the present invention is all greater than P2312 and EH-IQ, and especially at the low-temperature space below 50 ℃, difference is more obvious.

Life test:

Get 0.5ml EH-IQ and 0.5ml catalyst of the present invention and 0.5mlP2312 and carry out life test.50 ℃ of fixation reaction temperature, gas space velocity 3000h ^-1, other experimental condition is the same.The result as shown in Figure 1.

The result of Fig. 1 shows, catalyst of the present invention is through 186 hours running, actively do not change, and still up to 98%, EH-IQ then drops to about 80% from the conversion ratio 92% of COS, and P2312 drops to about 20% from 52%.Activity of such catalysts good stability of the present invention is described in EH-IQ and P2312, and explanation catalyst of the present invention can be used for transforming the COS unstripped gas of high concentration.

Embodiment:

Example 1:

Take by weighing 100 parts of boehmites, add 5 parts of metatitanic acids, 5 parts of kapoks are mixed, and add 1 part of 40 parts of water and 2 parts of red fuming nitric acid (RFNA)s, citric acid then, through extrusion, drying, roasting, make carrier ZT-1.Soaked 30 minutes in the KOH aqueous solution with ZT-1 immersion 5%, taking-up is being lower than 100 ℃ of dryings 15 hours, and repetitive operation is 2 times then, makes catalyst of the present invention, K ₂O content 10%.

Example 2:

Take by weighing 100 parts of boehmites, 10 parts of metatitanic acids add 3 parts of carboxymethyl celluloses, are mixed, and add 40 parts of entry then, 1 part of citric acid, and 1 part of red fuming nitric acid (RFNA) makes carrier ZT-2 through extrusion, drying, roasting.ZT-2 immersed in 10% the KOH aqueous solution 30 minutes, and took out the back at below 100 ℃ dry 10 hours, repetitive operation once makes and contains K ₂The COS hydrolyst of O12.5%.

Example 3

Take by weighing 100 parts of boehmites, 15 parts of metatitanic acids add 6 parts in sesbania powder, are mixed, and add 45 parts of entry, 1 part of red fuming nitric acid (RFNA), and 2 parts of citric acids get carrier ZT-3 through extrusion, drying, roasting.ZT-3 immersed in 5% the KOH aqueous solution and soak 2 times, and after soaking all under 85 ℃ of conditions dry 20 hours, make catalyst of the present invention, include K. at every turn ₂O7.5%.

Example 4:

Take by weighing 100 parts of boehmites, 10 parts of metatitanic acids add 6 parts of oxidized starch, are mixed, and add 45 parts of entry, 1 part of red fuming nitric acid (RFNA), and 1 part of citric acid through extrusion, drying, roasting, gets carrier ZT-4.ZT-4 was soaked 30 minutes in 5% the KOH aqueous solution,, in 10% the aqueous solution, soaks 2 times then, and through below 100 ℃ dry 20 hours through below 100 ℃ dry 15 hours, catalyst of the present invention, include K ₂O14%.

Example 5:

Take by weighing 100 parts of boehmites, 3 parts of metatitanic acids add 5 parts of carbonyl methyl celluloses, are mixed, and add 40 parts in water, 4 parts of red fuming nitric acid (RFNA)s, and 1 part of citric acid through extrusion, drying, roasting, gets carrier ZT-5.ZT-5 was soaked 30 minutes in 35% the KOH aqueous solution, through below 100 ℃ dry 15 hours, then catalyst of the present invention, include K ₂O15%.

Example 6:

Take by weighing 100 parts of boehmites, 3 parts of metatitanic acids add 4 parts in sesbania powder, are mixed, and add 40 parts in water, 8 parts of red fuming nitric acid (RFNA)s, and 2 parts of citric acids through extrusion, drying, roasting, get carrier ZT-6.ZT-6 was soaked 30 minutes in 5% the KOH aqueous solution, through 85 ℃ of dryings 15 hours, catalyst of the present invention, include K ₂O2%.

Example 7:

Take by weighing 100 parts of boehmites, 5 parts of metatitanic acids, 4 parts in lignin is mixed, and adds 45 parts in water, and 3 parts of red fuming nitric acid (RFNA)s through extrusion, drying, roasting, get carrier ZT-7.ZT-7 was soaked 30 minutes in 25% the KOH aqueous solution, through below 100 ℃ dry 20 hours, and once with 10% KOH aqueous solution repeated impregnations, must catalyst of the present invention, include K ₂O21%.

Claims

1, used normal temperature cos (COS) hydrolyst in a kind of petrochemical process, carrier is γ-Al ₂O ₃, active component is alkali-metal oxide, it is characterized in that:

Catalyst consists of:

γ-Al ₂O ₃98.5～55%(m/m)

TiO ₂1～20%(m/m)

KOH 0.5～25%(m/m)。

2, the preparation method of used normal temperature hydrolytic catalyst of carbonyl sulfur in a kind of petrochemical process, carrier is γ-Al ₂O ₃, active component is alkali-metal oxide, it is characterized in that:

Carry and make γ-Al ₂O ₃Pass through TiO ₂Modification, addition is 1～20%(m/m) of a finished catalyst, adds to do the mode of mixing at normal temperatures, earlier with boehmite, metatitanic acid, behind the pore creating material mixing, add entry and general glue and agent extruded moulding, dry under 100～150 ℃ by general method again, and at 500～700 ℃ of roasting temperatures, obtain catalyst carrier, and then dipping active component KOH0.5～25%(m/m).

3,, it is characterized in that described pore creating material is one or more the mixture in cellulose, lignin, sesbania powder, kapok, carboxymethyl cellulose, methylcellulose, hydroxyethylcellulose, oxidized starch, the enzyme starch by the described method of claim 2.