CN102463107A

CN102463107A - Method for preparing carbonyl sulfide hydrolysis catalysts

Info

Publication number: CN102463107A
Application number: CN2010105518752A
Authority: CN
Inventors: 肖忠斌; 畅延青
Original assignee: China Petroleum and Chemical Corp; Sinopec Shanghai Research Institute of Petrochemical Technology
Current assignee: China Petroleum and Chemical Corp; Sinopec Shanghai Research Institute of Petrochemical Technology
Priority date: 2010-11-17
Filing date: 2010-11-17
Publication date: 2012-05-23
Anticipated expiration: 2030-11-17
Also published as: CN102463107B

Abstract

The invention relates to a method for preparing carbonyl sulfide hydrolysis catalysts, which mainly solves the technical problems that the catalyst prepared by the existing preparation method has a narrow reaction temperature interval, and the application material gas air speed is low. The method for preparing the carbonyl sulfide hydrolysis catalysts adopts the technical scheme that the method comprises the following steps of: a) gamma-Al2O3 and rare earth oxide hydro-thermal treatment; b) still standing; c) drying; and d) forming. The problems are perfectly solved, and the method can be used for industrial production of the carbonyl sulfide hydrolysis catalysts.

Description

The preparation method of hydrolytic catalyst of carbonyl sulfur

Technical field

The present invention relates to a kind of preparation method of hydrolytic catalyst of carbonyl sulfur.

Background technology

It is in the chemical process of raw material that cos (COS) extensively is present in coal, oil, natural gas, and its existence is contaminated environment not only, and can cause catalyst poisoning in the subsequent production process, and product quality descends, equipment corrosion.Hydrolysis is to remove the most practical method of organic sulfur such as COS, and its process equation formula is: COS+H ₂O → H ₂S+CO ₂, organic sulfur is converted into easy-to-handle H ₂S is converted into S at last and reclaims.

U.S. Pat P4,455,446 disclose a kind of COS hydrolyst at the last load platinum sulfide of γ-Al2O3, will contain 0.08% platinum sulfide as reaction bed, can COS be dropped to below the 50ppb under 40 ℃, and weak point is that the catalyst cost is high.

U.S. Pat P4,511,668 disclose a kind of with TiO ₂Be carrier, contain a kind of alkali metal, alkaline-earth metal COS hydrolyst at least as active component, with activity component impregnation to the carrier that contains 93%TiO2,4% SiO2,3% γ-Al2O3, then at 120 ℃ of dry 1h, 500 ℃ of calcining 3h then.But this catalyst is in use handled unstripped gas COS content and is merely 73ppm, and reaction temperature is higher, is 200～400 ℃.

Chinese patent CN1069673 discloses a kind of normal tempreture organic sulphur hydrolysis catalyst, and it is at spherical gamma-Al ₂O ₃Last load 2～5%K ₂CO ₃, its preparation method is with γ-Al ₂O ₃Carrier is with K ₂CO ₃The aqueous solution is impregnated on the carrier, K ₂CO ₃After content reaches requirement, in room temperature to 120 ℃ following drying.The weak point of this catalyst is that unstripped gas COS content and air speed are all lower, is respectively 1～5mg/m ³With 2,000hr ^-1

Chinese patent CN1134312 discloses a kind of by 4～20wt%TiO ₂And γ-Al ₂O ₃The organic sulfur hydrolyst of forming, its preparation method are that the aluminium hydroxide of refinement treatment and titanium hydroxide are mixed the back roller forming in proportion.Handle semi-finished product ball, activated, calcining again with special cleaning solution.The weak point of this catalyst is that air speed is merely 1,800hr ^-1

Chinese patent CN1304781 discloses a kind of 83～97% γ-Al that consists of ₂O ₃, 2～25%K ₂The COS hydrolyst of O, 0.12BaO, its preparation method is with γ-Al ₂O ₃Carrier is with K ₂CO ₃The aqueous solution is impregnated into K on the carrier ₂CO ₃After content reaches requirement, in room temperature to 120 ℃ following drying.Less than 150 ℃, COS content is less than 800mg/m3 in temperature, air speed 6,000～9,000hr ^-1Carry out desulfurization under the condition, the COS hydrolysis conversion is greater than 95%.

The weak point of the catalyst that above-mentioned prior art provides is: the reaction temperature interval of COS hydrolysis is narrower, and the unstripped gas air speed is low.

Summary of the invention

Technical problem to be solved by this invention is that the catalyst reaction temperatures interval of existing preparation method's preparation is narrow; The problem of applicable raw materials gas air speed narrow range; A kind of preparation method of new hydrolytic catalyst of carbonyl sulfur is provided; The catalyst of this method preparation is used for the carbonyl sulfide hydrolysis reaction, has the characteristics that reaction temperature is wide, adapt to higher unstripped gas air speed concurrently.

In order to solve the problems of the technologies described above, the technical scheme that the present invention adopts is following: a kind of preparation method of hydrolytic catalyst of carbonyl sulfur comprises the steps: a) γ-Al ₂O ₃With the rare earth oxide hydrothermal treatment consists; B) leave standstill; C) drying; D) moulding.

In the technique scheme, the condition preferable range of step a) hydrothermal treatment consists is 60～100 ℃ and 2～8 hours; The time of repose preferable range of step b) is 8～15 hours; The dry condition preferable range of step c) is 100～130 ℃ and 10～24 hours; The forming method preferred version of step d) is the pressed disc method moulding.

Certainly, the forming method in the technique scheme is not limited to compression molding, also can adopt forming methods well known in the art such as rolling moulding, extrusion molding.

The inventive method is except comprising above-mentioned step a)～d); Can also comprise other steps; For example, in order to reduce the abrasion and the powder that falls in the processes such as accumulating, operation, can also after moulding, increase a polishing step well known to those of ordinary skill in the art etc.

Key problem in technology of the present invention is in Preparation of catalysts, to have adopted rare earth oxide, thereby because the interaction of rare earth oxide and aluminium oxide makes catalyst provided by the invention have the characteristic that reaction temperature is wide, adapt to higher unstripped gas air speed concurrently.Adopt the inventive method to make catalyst, its temperature accommodation is 80～250 ℃, and the unstripped gas air speed can be up to 20,000hr ^-1, obtained better technical effect.

Through embodiment the present invention is done further elaboration below.

The specific embodiment

[embodiment 1]

Preparation of Catalyst: take by weighing the pulverous γ-Al of 90g respectively ₂O ₃With the Powdered La of 10g ₂O ₃, adding the 800ml deionized water, hydrothermal treatment consists is 8 hours under 60 ℃ of conditions, leaves standstill 8 hours; 110 ℃ of dryings 18 hours, compressing tablet, fragmentation, sieve were got 40～60 purpose samples and are obtained required catalyst then.For ease of comparing, catalyst formulation and preparation condition are as shown in table 1.

Evaluating catalyst: estimate and in Φ 10 * 300 fixed bed quartz tube reactors, carry out, temperature is 80 ℃, COS content 100ppm, mol ratio H ₂O: COS is 10, air speed 10,000hr ^-1For ease of comparing, the appreciation condition and the evaluation result of catalyst are as shown in table 2.

[embodiment 2～9]

Catalyst formulation and preparation condition are as shown in table 1, and the appreciation condition and the evaluation result of catalyst are as shown in table 2, and not specified factor is all identical with [embodiment 1] in table 1 and the table 2.

[embodiment 10]

Getting the 1 prepared catalyst by embodiment, is under the 150ppm condition except temperature at 100-250 ℃ of variation, COS content in evaluation test, and in addition, other appreciation condition is all identical with [embodiment 1], and the COS conversion ratio is as shown in table 3.

Table 1 catalyst formulation and preparation condition

Table 2 catalyst activity appreciation condition and COS conversion ratio

	Temperature (℃)	Air speed (h ^-1)	COS concentration (ppm)	COS conversion ratio (%)
					Embodiment 1	80	10,000	100	90.5
Embodiment 2	100	10,000	150	95.8
					Embodiment 3	120	15,000	150	98.2
Embodiment 4	150	15,000	150	99.1
					Embodiment 6	200	10,000	200	99.4
Embodiment 7	200	15,000	250	99.2
					Embodiment 8	200	15,000	200	99.9
Embodiment 9	250	20,000	300	99.5

Table 3 air speed is to the influence of Catalyst for CO S hydrolysing activity

Temperature, ℃	100	150	200	250
					COS conversion ratio %	98.8	99.0	99.5	99.9

Claims

1. the preparation method of a hydrolytic catalyst of carbonyl sulfur comprises the steps: a) γ-Al ₂O ₃With the rare earth oxide hydrothermal treatment consists; B) leave standstill; C) drying; D) moulding.

2. Preparation of catalysts method as claimed in claim 1, the condition that it is characterized in that said step a) hydrothermal treatment consists are 60～100 ℃ and 2～8 hours.

3. Preparation of catalysts method as claimed in claim 1, the time of repose that it is characterized in that said step b) is 8～15 hours.

4. Preparation of catalysts method as claimed in claim 1 is characterized in that the dry condition of said step c) is 100～130 ℃ and 10～24 hours.

5. Preparation of catalysts method as claimed in claim 1, what it is characterized in that said step d) is shaped to the pressed disc method moulding.