CN102463107B

CN102463107B - Method for preparing carbonyl sulfide hydrolysis catalysts

Info

Publication number: CN102463107B
Application number: CN201010551875.2A
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: 2014-07-23
Anticipated expiration: 2030-11-17
Also published as: CN102463107A

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

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

US Patent No. P4,455,446 disclose a kind of on γ-Al2O3 the COS hydrolyst of load platinum sulfide, will be containing 0.08% platinum sulfide as reaction bed, COS can be dropped to below 50ppb at 40 DEG C, weak point is that catalyst cost is high.

US Patent No. P4,511,668 disclose one with TiO ₂for carrier, at least COS hydrolyst as active component containing a kind of alkali metal, alkaline-earth metal, by activity component impregnation to the carrier that contains 93%TiO2,4% SiO2,3% γ-Al2O3, then at 120 DEG C of dry 1h, then 500 DEG C of calcining 3h.But it is only 73ppm that this catalyst is in use processed unstripped gas COS content, and reaction temperature is higher, is 200～400 DEG C.

Chinese patent CN1069673 discloses a kind of normal tempreture organic sulphur hydrolysis catalyst, and it is at spherical gamma-Al ₂o ₃upper load 2～5%K ₂cO ₃, its preparation method is by γ-Al ₂o ₃carrier is with K ₂cO ₃the aqueous solution is impregnated on carrier, K ₂cO ₃content reaches after requirement, dry at room temperature to 120 DEG C.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 composition, its preparation method is that the aluminium hydroxide of refinement treatment and titanium hydroxide are mixed to rear roller forming in proportion.Process semi-finished product ball, activated, calcining again with special cleaning solution.The weak point of this catalyst is that air speed is only 1,800hr ^-1.

Chinese patent CN1304781 discloses one and has consisted of 83～97% γ-Al ₂o ₃, 2～25%K ₂the COS hydrolyst of O, 0.12BaO, its preparation method is by γ-Al ₂o ₃carrier is with K ₂cO ₃the aqueous solution is impregnated into K on carrier ₂cO ₃content reaches after requirement, dry at room temperature to 120 DEG C.Be less than 150 DEG C in temperature, COS content is less than 800mg/m3, air speed 6,000～9,000hr ^-1under condition, carry out desulfurization, 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 unstripped gas air speed is low.

Summary of the invention

Technical problem to be solved by this invention is that the existing preparation method catalyst reaction temperatures interval of preparing 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, catalyst prepared by the method reacts for carbonyl sulfide hydrolysis, has the feature 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 solution used in the present invention is as follows: a kind of preparation method of hydrolytic catalyst of carbonyl sulfur, comprises the steps: a) by γ-Al ₂o ₃with rare earth oxide hydrothermal treatment consists; B) leave standstill; C) dry; D) moulding.

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

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

The inventive method except comprise above-mentioned a)～step d), can also comprise other steps, for example, in order to reduce abrasion and the powder falling in the process 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 to have adopted rare earth oxide in the preparation of catalyst, thereby has because the interaction of rare earth oxide and aluminium oxide makes catalyst provided by the invention 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 DEG C, and unstripped gas air speed can be up to 20,000hr ^-1, obtained good technique effect.

Below by embodiment, the present invention is further elaborated.

Detailed description of the invention

[embodiment 1]

Catalyst preparation: take respectively the pulverous γ-Al of 90g ₂o ₃with the Powdered La of 10g ₂o ₃, add 800ml deionized water, 60 DEG C of Water Under heat treatments 8 hours, leave standstill 8 hours; Then be dried 18 hours at 110 DEG C, compressing tablet, fragmentation, sieve are got 40～60 object samples and are obtained required catalyst.For ease of comparing, catalyst formulation and preparation condition are as shown in table 1.

Evaluating catalyst: evaluate and carry out in Φ 10 × 300 fixed bed quartz tube reactors, temperature is 80 DEG C, COS content 100ppm, mol ratio H ₂o: COS is 10, air speed 10,000hr ^-1.For ease of comparing, 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 appreciation condition and the evaluation result of catalyst are as shown in table 2, and in table 1 and table 2, not specified factor is all identical with [embodiment 1].

[embodiment 10]

Get the prepared catalyst by embodiment 1, in evaluation test, except temperature is under 150ppm condition at 100-250 DEG C of variation, COS content, in addition, other appreciation condition is all identical with [embodiment 1], and 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 (DEG C)	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

The impact of table 3 air speed on Catalyst for CO S hydrolysing activity

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

Claims

1. a preparation method for hydrolytic catalyst of carbonyl sulfur, comprises the steps: to take respectively the pulverous γ-A1 of 85g ₂o ₃, 5gEu ₂o ₃, 5gSm ₂o ₃, 5gGd ₂o ₃, add 800ml deionized water, 90 DEG C of Water Under heat treatments 4 hours, leave standstill 10 hours; Then be dried 18 hours at 110 DEG C, compressing tablet, fragmentation, sieve are got 40～60 object samples and are obtained required catalyst.