CN103480355B - Organic sulfur hydrolysis catalyst applicable to natural gas large-scale sulfur recovery device and preparation method thereof - Google Patents

Abstract

The invention is an organic sulfur hydrolysis catalyst applicable to a natural gas large-scale sulfur recovery device and a preparation method thereof, and belongs to a method of removing sulfur compounds in mixed gas by a catalytic method. The catalyst comprises a catalyst carrier and a catalyst active component, and is characterized in that the carrier is composed of Al2O3 and CaO, and the active component is K2O. The catalyst comprises the following chemical substances in parts by weight: 78.0-97.9 parts of Al2O3, 0.1-2.0 parts of CaO, and 2.0-20.0 parts of K2O. Provided is the organic sulfur hydrolysis catalyst used in the natural gas large-scale sulfur recovery device, wherein the catalyst has large specific surface area, large pore volume and high low-temperature organic sulfur hydrolysis activity. The specific surface area of the catalyst is greater than 300 m<2>/g, the pore volume of the catalyst is greater than 0.35 ml/g, and thus the catalyst is ensured to have good catalytic activity. With the use of the catalyst and under certain conditions, the hydrolysis rate of organic sulfur in natural gas can reach 99% or more, and can meet sulfur compound removal technical requirements of the large-scale sulfur recovery device in natural gas purification industry. Moreover, natural gas products are ensured to reach technical indexes stipulated by national standards.

Description

Be applicable to organic sulfur hydrolyst of natural gas large-scale sulfur recovery device and preparation method thereof

Technical field

The present invention is a kind ofly applicable to organic sulfur hydrolyst of natural gas large-scale sulfur recovery device and preparation method thereof.Belong to the method adopting catalysis process to remove sulphur compound in mist.

Background technology

The ratio of natural gas in world's primary energy consumption structure reaches about 25%, and exceeding coal becomes second, has become a kind of important energy sources.At present, in gas purifying process, sulfur recovery facility mainly adopts the technique such as claus process and a small amount of Selextox, and exhaust gas processing device mainly adopts the techniques such as SCOT, CBA and MCRC.Along with the continuous expansion of gas production, purifying device for natural gas, the scale as sulfur recovery facility is increasing, and sulfur recovery facility maximization is developing direction from now on.Because operating cost can be reduced, improve economic benefit and the environmental protection benefit of enterprise.。

According to the requirement of the strategy of sustainable development and environmental protection state basic policy, China greatly develops gas industry, and some new high-sulfur Large gas fields are developed in succession, and this just proposes new demand to gas purifying process.At present, Zhongyuan Oil Field branch company of China Petrochemical Industry general phosgene field Gas Purification Factory is the maximum gas purification plant of China, it is the sulfur recovery facility of 200kt/a that this factory has 12 cover list cover scales, device adopts the technique bag of Black & Veatch company of the U.S., matching used catalyst is import, imported catalyst is expensive, changes a catalyst cost huge.

Because in natural gas, organic sulfur content is higher, generally organic sulfur hydrolysis unit is set separately before Claus unit.Such as, the general smooth Gas Purification Factory of China Petrochemical Industry just arranges organic sulfur hydrolysis unit in sulfur recovery unit front portion, to reduce the content of organic sulfur in natural gas.Owing to containing a certain amount of carbon dioxide in natural gas, the hydrolysis of existence to organic sulfur of carbon dioxide has certain inhibitory action, this just requires that the catalytic activity of the organic sulfur hydrolyst used at natural-gas sulphur retracting device is compared other devices and wanted high, otherwise cannot meet the requirement of device.Both at home and abroad, the organic sulfur hydrolyst that large-scale sulfur recovery device uses is generally the PURASPEC-2312 catalyst that ten thousand rich (Johnson Matthey) company is believed in the Britain village, this catalyst take aluminium oxide as main component, have the advantages that specific area is large, hydrolysis effect is good, but low temperature hydrolysis activity is slightly poor.At present, exploitation has the catalyst of good low temperature tempreture organic sulphur hydrolysis activity, and the requirement meeting large-scale natural gas field sulfur recovery unit is the developing direction of such catalyst.

CN00119385.6 describes a kind of hydrolytic catalyst of carbonyl sulfur, and it consists of γ-Al ₂o ₃83% ~ 97%, K ₂o 2% ~ 15%, BaO 0.1% ~ 2%.This catalyst adopts equal-volume solution dipping method to be prepared, and its purposes is temperature 80 ~ 150 DEG C, and normal pressure, COS content is less than 800mg/m ³, air speed 6000 ~ 9000h ^-1desulfurization is carried out under condition.The catalyst serviceability temperature of this patented invention is higher, generally more than 80 DEG C, can not meet low temperature instructions for use.

CN201010556207.9 describes a kind of catalyst for removing cos in Chemical Manufacture unstripped gas, and especially relating to a kind of component is magnesium-aluminum-based hydrotalcite, γ-Al ₂o ₃, TiO ₂cOS hydrolyst and preparation method thereof.By γ-Al ₂o ₃, TiO ₂mix with magnesium-aluminum-based hydrotalcite, add water kneading, extruded moulding, drying, roasting, obtained hydrolytic catalyst of carbonyl sulfur product.The catalyst carrier of this patented invention is titanium aluminium complex carrier, and preparation cost is high.

The organic sulfur hydrolyst being applicable to natural gas large-scale sulfur recovery device at present also there is not yet reported in literature.

Summary of the invention

The object of the invention is to avoid above-mentioned weak point of the prior art, and provide a kind of and have that specific surface is large, pore volume is large, the active high organic sulfur hydrolyst for natural gas large-scale sulfur recovery device of low temperature tempreture organic sulphur hydrolysis.Adopt large-scale sulfur recovery device to process in natural gas in order to solve, the problem that the organic sulfur content run into is higher, meets the quality requirement that natural gas dispatches from the factory.

The present invention also aims to the preparation method being applicable to the organic sulfur hydrolyst of natural gas large-scale sulfur recovery device providing a kind of preparation cost lower.

Object of the present invention can be reached by following measure:

The organic sulfur hydrolyst being applicable to natural gas large-scale sulfur recovery device of the present invention, comprises catalyst carrier and catalyst activity component, it is characterized in that carrier is by Al ₂o ₃with calcium oxide composition, active component is potassium oxide, and catalyst is as follows with the chemical substance of weight parts composition:

Al ₂O ₃78.0～97.9

CaO 0.1～2.0

K ₂O 2.0～20.0

Described carrier is with the fast shedding of aluminium hydroxide for body material, and interpolation aluminum hydroxide solid elastomer and calcium oxide, as modified additive, add appropriate binding agent, adopts roller forming, slaking, drying, roasting, makes; Al in carrier ₂o ₃component is provided by the fast shedding of aluminium hydroxide and aluminum hydroxide solid elastomer, and the two parts by weight ratio is:

The fast shedding of aluminium hydroxide is with Al ₂o ₃meter 100

Aluminum hydroxide solid elastomer is with Al ₂o ₃meter 5.0 ~ 100

CaO in described carrier adds with the form of Paris white or calcium oxide powder;

Described binding agent is any one in acetic acid, nitric acid, citric acid, Alumina gel;

Wherein, the fast shedding specific surface of aluminium hydroxide is greater than 250m ²/ g, pore volume are greater than 0.20ml/g; Aluminum hydroxide solid elastomer specific surface is greater than 350m ²/ g, pore volume are greater than 0.70ml/g;

Described active component K ₂o is with by potash and potassium hydroxide aqueous solution, and the mode be impregnated in catalyst carrier adds, and the mol ratio of potash and potassium hydroxide is 1:1 ~ 5:1.

Owing to containing a certain amount of carbon dioxide in natural gas, the hydrolysis of existence to organic sulfur of carbon dioxide has certain inhibitory action, and this compares with regard to the catalyst activity requiring gas plant to use and wants high.The present invention is characterized in that catalyst carrier is using the fast shedding of aluminium hydroxide as raw material, adds aluminum hydroxide solid elastomer and calcium oxide is prepared from as auxiliary agent, to improve the hydrolysing activity of catalyst simultaneously.What the active constituent of catalyst used be the alkali metal that alkalescence is stronger, and catalyst prepared by the present invention has that specific surface is large, pore volume large, low temperature tempreture organic sulphur hydrolysis activity advantages of higher.The specific surface of catalyst of the present invention is greater than 300m ²/ g, pore volume are greater than 0.35ml/g, ensure that catalysis has good catalytic activity.Use this catalyst under certain condition in natural gas the percent hydrolysis of organic sulfur can reach more than 99%, organic sulfur content in natural gas is significantly declined.Therefore, this catalyst can meet the technical requirement of the sulfur recovery unit of natural gas purification industry.

Object of the present invention can also be reached by following measure:

The of the present invention organic sulfur hydrolyst being applicable to natural gas large-scale sulfur recovery device, is characterized in that carrier is by Al ₂o ₃with calcium oxide composition, active component is potassium oxide, and catalyst is as follows with the chemical substance of weight parts composition:

Al ₂O ₃9.0～95.5

CaO 0.5～1.0

K ₂O 4.0～10.0

Described carrier is with the fast shedding of aluminium hydroxide for body material, and interpolation aluminum hydroxide solid elastomer and calcium oxide, as modified additive, add appropriate binding agent, adopts roller forming, slaking, drying, roasting, makes; Al in carrier ₂o ₃component is provided by the fast shedding of aluminium hydroxide and aluminum hydroxide solid elastomer, and the two parts by weight ratio is:

The fast shedding of aluminium hydroxide is with Al ₂o ₃meter 100

Aluminum hydroxide solid elastomer is with Al ₂o ₃meter 10 ~ 60

Described binding agent is acetic acid;

Wherein, the fast shedding Al of aluminium hydroxide ₂o ₃content>=70%, specific surface is greater than 300m ²/ g, pore volume are greater than 0.35ml/g; Aluminum hydroxide solid elastomer Al ₂o ₃content>=70%, specific surface is greater than 400m ²/ g, pore volume are greater than 0.90ml/g;

Described active component K ₂o is with by potash and potassium hydroxide aqueous solution, and the mode be impregnated in catalyst carrier adds, and the mol ratio of potash and potassium hydroxide is 3:1.

It is preferred technical scheme.

The preparation method being applicable to the organic sulfur hydrolyst of natural gas large-scale sulfur recovery device of the present invention, is characterized in that comprising the steps:

1. the preparation of catalyst carrier:

A. aluminum hydroxide solid elastomer dehydrates

The dry glue of raw aluminum hydroxide, under temperature is 450 ~ 650 DEG C of conditions, dehydrates 1 ~ 2 hour, for subsequent use;

B. batch mixing

By fast for the raw aluminum hydroxide of formula ratio shedding and the aluminum hydroxide solid elastomer dehydrated through step a, calcium oxide mixes, as the support material of Kaolinite Preparation of Catalyst, for subsequent use;

C. the preparation of binder solution A

Mix the amount of material according to step b, take appropriate binding agent, add suitable quantity of water, stir, for subsequent use;

D roller forming

The a part of raw material mixed through step b is put into bowling machine, and open bowling machine, spray the binder solution A prepared through step c to the material in bowling machine, material rolls and is shaped to small spheric granules under binder solution A effect; After forming particle, continue to add raw material, while interpolation raw material, continue spray solution A, until the raw material overwhelming majority is shaped to diameter bead, stop operating.Sieved by spheric granules, taking out diameter is bead, standby slaking;

E slaking

Steps d is shaping bead, control in the steam atmosphere of 40 ~ 100 DEG C, slaking 10 ~ 40 hours;

F. dry

By through step e slaking bead, control at 80 ~ 160 DEG C of temperature, dry 3 ~ 5 hours;

G. roasting

By through step f drying bead, control at 350 ~ 500 DEG C of temperature, roasting 2 ~ 10 hours, i.e. obtained catalyst carrier.

2. the preparation of catalyst

Catalyst adopts equi-volume impregnating preparation, comprises the steps:

A. the preparation of activity component impregnation liquid

According to following ratio:

Al ₂O ₃78.0～97.9

CaO 0.1～2.0

K ₂O 2.0～20.0

Take potash and potassium hydroxide, the mol ratio controlling potash and potassium hydroxide is 1:1 ~ 5:1; Be dissolved in appropriate amount of deionized water, stir formation stabilizing solution, and namely the addition constant volume according to carrier obtains activity component impregnation liquid, for subsequent use;

B. carrier impregnation

According to equi-volume impregnating, the pre-preg carrier measured is joined in activity component impregnation liquid prepared by step a, flood 10 minutes ~ 3 hours;

C. dry

The carrier flooded by step b, controls 110 ~ 150 DEG C, dries 2 ~ 6 hours;

D. roasting

By carrier dried for step c, control 350 ~ 700 DEG C of roastings 2 ~ 10 hours; The organic sulfur hydrolyst product of natural gas large-scale sulfur recovery device must be applicable to.

The present inventor is applicable to the inventive concept of the organic sulfur hydrolyst component of natural gas large-scale sulfur recovery device according to development, well-designed with match, easy to operate, the lower-cost preparation method of formula, thus complete task of the present invention, achieve beyond thought technique effect.

The preparation method being applicable to the organic sulfur hydrolyst of natural gas large-scale sulfur recovery device of the present invention, comprises the steps:

1. the preparation of catalyst carrier:

A. aluminum hydroxide solid elastomer dehydrates

The dry glue of raw aluminum hydroxide, under temperature is 500 ~ 600 DEG C of conditions, dehydrates 1 ~ 2 hour, for subsequent use;

B. batch mixing

By fast for the raw aluminum hydroxide of formula ratio shedding and the aluminum hydroxide solid elastomer dehydrated through step a, calcium oxide mixes, as the support material of Kaolinite Preparation of Catalyst, for subsequent use;

C. the preparation of binder solution A

Mix the amount of material according to step b, take appropriate binding agent, add suitable quantity of water, stir, for subsequent use;

D roller forming

The a part of raw material mixed through step b is put into bowling machine, and open bowling machine, spray the binder solution A prepared through step c to the material in bowling machine, material rolls and is shaped to small spheric granules under binder solution A effect; After forming particle, continue to add raw material, while interpolation raw material, continue spray solution A, until the raw material overwhelming majority is shaped to diameter bead, stop operating.Sieved by spheric granules, taking out diameter is bead, standby slaking;

E slaking

Steps d is shaping bead, control in the steam atmosphere of 80 ~ 100 DEG C, slaking 10 ~ 40 hours;

F. dry

By through step e slaking bead, control at 110 ~ 130 DEG C of temperature, dry 3 ~ 5 hours;

G. roasting

By through step f drying bead, control at 380 ~ 450 DEG C of temperature, roasting 3 ~ 5 hours, i.e. obtained catalyst carrier.

2. the preparation of catalyst

Catalyst adopts equi-volume impregnating preparation, comprises the steps:

A. the preparation of activity component impregnation liquid

According to following ratio:

Al ₂O ₃89.0～95.5

CaO 0.5～1.0

K ₂O 4.0～10.0

Take potash and potassium hydroxide, the mol ratio controlling potash and potassium hydroxide is 3:1; Be dissolved in appropriate amount of deionized water, stir formation stabilizing solution, and namely the addition constant volume according to carrier obtains activity component impregnation liquid, for subsequent use;

B. carrier impregnation

According to equi-volume impregnating, the pre-preg carrier measured is joined in activity component impregnation liquid prepared by step a, flood 10 minutes ~ 3 hours;

C. dry

The carrier flooded by step b, controls 110 ~ 150 DEG C, dries 2 ~ 6 hours;

D. roasting

By carrier dried for step c, control 500 ~ 600 DEG C of roastings 2 ~ 10 hours; The organic sulfur hydrolyst product of natural gas large-scale sulfur recovery device must be applicable to.

It is a preferred technical scheme disclosed in inventor.

The application being applicable to the organic sulfur hydrolyst of natural gas large-scale sulfur recovery device of the present invention, is characterized in that the tempreture organic sulphur hydrolysis process being applicable to natural gas large-scale sulfur recovery device.

Of the present inventionly be applicable to organic sulfur hydrolyst of natural gas large-scale sulfur recovery device and preparation method thereof, have following good effect compared to existing technology:

1. provide a kind ofly have that specific surface is large, pore volume is large, the active high organic sulfur hydrolyst for natural gas large-scale sulfur recovery device of low temperature tempreture organic sulphur hydrolysis.

2. provide a kind of easy to operate, lower-cost preparation method being applicable to the organic sulfur hydrolyst of natural gas large-scale sulfur recovery device.

3. the specific surface of catalyst of the present invention is greater than 300m ²/ g, pore volume are greater than 0.35ml/g, ensure that catalysis has good catalytic activity.Use this catalyst under certain condition in natural gas the percent hydrolysis of organic sulfur can reach more than 99%, organic sulfur content in natural gas is significantly declined.Therefore, this catalyst can meet the technical requirement of the sulfur recovery unit of natural gas purification industry.

4. catalyst of the present invention can meet the technical requirement of the removal of sulfur compounds of natural gas purification industry large-scale sulfur recovery device.And ensure that gas product be up to state standards regulation technical indicator.

Accompanying drawing explanation

Fig. 1 is catalyst preparing schematic flow sheet of the present invention

Fig. 2 is laboratory catalytic agent activity rating device schematic flow sheet

In figure:

1-CO2 gas cylinder, 2-COS gas cylinder, 3-N ₂gas cylinder, 4-water bottle, 5-mass flowmenter, 6-pump, 7-reactor, 8-amasss sulphur device, 9-cold-trap, 10-caustic treater, 11-chromatogram, the emptying of 12-tail gas.

Detailed description of the invention

The present invention will now be further detailed embodiment:

Embodiment 1

Taking specific surface is 422m ²the aluminum hydroxide solid elastomer 1 kilogram of/g, pore volume 1.10ml/g is positioned in roaster, dehydrates 2 hours at 550 DEG C.Taking 4 kilograms of specific surfaces is 320m ²the fast shedding of aluminium hydroxide and 50 grams of purity of/g, pore volume 0.41ml/g are the calcium oxide of 99%, mix with the aluminum hydroxide solid elastomer after dehydration.

Take the acetic acid 402 grams that purity is 99.5%, dissolved in water, stir, be configured to binding agent.The solid material mixed is placed in bowling machine, the binding agent prepared slowly is sprayed in the solid material mixed, rotate roller forming, obtain catalyst pellet, by bead under the water vapour atmosphere of 100 DEG C slaking 20 hours, 120 DEG C dry 4 hours, 400 DEG C roastings within 3 hours, can catalyst carrier be obtained.Catalyst activity component is potassium oxide, taking 483 grams, potash dissolves in deionized water with 33.6 grams, potassium hydroxide, stir formation stabilizing solution, namely addition constant volume according to carrier obtains activity component impregnation liquid, according to equi-volume impregnating impregnated catalyst, the catalyst of preparation is dried 4 hours, 550 DEG C roastings at 120 DEG C and can be obtained finished catalyst in 3 hours, and obtained specific surface is 321m ²/ g, pore volume 0.37ml/g.

Embodiment 2

Taking specific surface is 422m ²the aluminum hydroxide solid elastomer 1 kilogram of/g, pore volume 1.10ml/g is positioned in roaster, dehydrates 2 hours at 550 DEG C.Taking 5 kilograms of specific surfaces is 320m ²the fast shedding of aluminium hydroxide and 60 grams of purity of/g, pore volume 0.41ml/g are the calcium oxide of 99%, mix with the aluminum hydroxide solid elastomer after dehydration.

Take the acetic acid 402 grams that purity is 99.5%, dissolved in water, stir, be configured to binding agent.The solid material mixed is placed in bowling machine, the binding agent prepared slowly is sprayed in the solid material mixed, rotate roller forming, obtain catalyst pellet, by bead under the water vapour atmosphere of 100 DEG C slaking 20 hours, 120 DEG C dry 4 hours, 400 DEG C roastings within 3 hours, can catalyst carrier be obtained.Catalyst activity component is potassium oxide, taking 483 grams, potash dissolves in deionized water with 33.6 grams, potassium hydroxide, stir formation stabilizing solution, namely addition constant volume according to carrier obtains activity component impregnation liquid, according to equi-volume impregnating impregnated catalyst, the catalyst of preparation is dried 4 hours, 550 DEG C roastings at 120 DEG C and can be obtained finished catalyst in 3 hours, and obtained specific surface is 315m ²/ g, pore volume 0.36ml/g.

Embodiment 3

Taking specific surface is 422m ²the aluminum hydroxide solid elastomer 1 kilogram of/g, pore volume 1.10ml/g is positioned in roaster, dehydrates 2 hours at 550 DEG C.Taking 4 kilograms of specific surfaces is 320m ²the fast shedding of aluminium hydroxide and 50 grams of purity of/g, pore volume 0.41ml/g are the calcium oxide of 99%, mix with the aluminum hydroxide solid elastomer after dehydration.

Take the acetic acid 402 grams that purity is 99.5%, dissolved in water, stir, be configured to binding agent.The solid material mixed is placed in bowling machine, the binding agent prepared slowly is sprayed in the solid material mixed, rotate roller forming, obtain catalyst pellet, by bead under the water vapour atmosphere of 100 DEG C slaking 20 hours, 120 DEG C dry 4 hours, 400 DEG C roastings within 3 hours, can catalyst carrier be obtained.Catalyst activity component is potassium oxide, taking 511 grams, potash dissolves in deionized water with 22.4 grams, potassium hydroxide, stir formation stabilizing solution, namely addition constant volume according to carrier obtains activity component impregnation liquid, according to equi-volume impregnating impregnated catalyst, the catalyst of preparation is dried 4 hours, 550 DEG C roastings at 120 DEG C and can be obtained finished catalyst in 3 hours, and obtained specific surface is 323m ²/ g, pore volume 0.37ml/g.

Embodiment 4

Taking specific surface is 422m ²the aluminum hydroxide solid elastomer 1 kilogram of/g, pore volume 1.10ml/g is positioned in roaster, dehydrates 2 hours at 550 DEG C.Taking 4 kilograms of specific surfaces is 320m ²the fast shedding of aluminium hydroxide and 50 grams of purity of/g, pore volume 0.41ml/g are the calcium oxide of 99%, mix with the aluminum hydroxide solid elastomer after dehydration.

Take the acetic acid 402 grams that purity is 99.5%, dissolved in water, stir, be configured to binding agent.The solid material mixed is placed in bowling machine, the binding agent prepared slowly is sprayed in the solid material mixed, rotate roller forming, obtain catalyst pellet, by bead under the water vapour atmosphere of 100 DEG C slaking 20 hours, 120 DEG C dry 4 hours, 400 DEG C roastings within 3 hours, can catalyst carrier be obtained.Catalyst activity component is potassium oxide, taking 552 grams, potash dissolves in deionized water with 37.5 grams, potassium hydroxide, stir formation stabilizing solution, namely addition constant volume according to carrier obtains activity component impregnation liquid, according to equi-volume impregnating impregnated catalyst, the catalyst of preparation is dried 4 hours, 550 DEG C roastings at 120 DEG C and can be obtained finished catalyst in 3 hours, and obtained specific surface is 317m ²/ g, pore volume 0.37ml/g.

Embodiment 5

Taking specific surface is 422m ²the aluminum hydroxide solid elastomer 1 kilogram of/g, pore volume 1.10ml/g is positioned in roaster, dehydrates 2 hours at 550 DEG C.Taking 4 kilograms of specific surfaces is 320m ²the fast shedding of aluminium hydroxide and 50 grams of purity of/g, pore volume 0.41ml/g are the calcium oxide of 99%, mix with the aluminum hydroxide solid elastomer after dehydration.

Take the acetic acid 402 grams that purity is 99.5%, dissolved in water, stir, be configured to binding agent.The solid material mixed is placed in bowling machine, the binding agent prepared slowly is sprayed in the solid material mixed, rotate roller forming, obtain catalyst pellet, by bead under the water vapour atmosphere of 100 DEG C slaking 20 hours, 120 DEG C dry 4 hours, 400 DEG C roastings within 3 hours, can catalyst carrier be obtained.Catalyst activity component is potassium oxide, taking 270 grams, potash dissolves in deionized water with 18 grams, potassium hydroxide, stir formation stabilizing solution, namely addition constant volume according to carrier obtains activity component impregnation liquid, according to equi-volume impregnating impregnated catalyst, the catalyst of preparation is dried 4 hours, 550 DEG C roastings at 120 DEG C and can be obtained finished catalyst in 3 hours, and obtained specific surface is 326m ²/ g, pore volume 0.37ml/g.

Embodiment 6

Taking specific surface is 422m ²the aluminum hydroxide solid elastomer 0.6 kilogram of/g, pore volume 1.10ml/g is positioned in roaster, dehydrates 2 hours at 550 DEG C.Taking 4.4 kilograms of specific surfaces is 320m ²the fast shedding of aluminium hydroxide and 50 grams of purity of/g, pore volume 0.41ml/g are the calcium oxide of 99%, mix with the aluminum hydroxide solid elastomer after dehydration.

Take the acetic acid 402 grams that purity is 99.5%, dissolved in water, stir, be configured to binding agent.The solid material mixed is placed in bowling machine, the binding agent prepared slowly is sprayed in the solid material mixed, rotate roller forming, obtain catalyst pellet, by bead under the water vapour atmosphere of 100 DEG C slaking 20 hours, 120 DEG C dry 4 hours, 400 DEG C roastings within 3 hours, can catalyst carrier be obtained.Catalyst activity component is potassium oxide, taking 483 grams, potash dissolves in deionized water with 33.6 grams, potassium hydroxide, stir formation stabilizing solution, namely addition constant volume according to carrier obtains activity component impregnation liquid, according to equi-volume impregnating impregnated catalyst, the catalyst of preparation is dried 4 hours, 550 DEG C roastings at 120 DEG C and can be obtained finished catalyst in 3 hours, and obtained specific surface is 309m ²/ g, pore volume 0.35ml/g.

Embodiment 7

Taking specific surface is 422m ²the aluminum hydroxide solid elastomer 1.6 kilograms of/g, pore volume 1.10ml/g is positioned in roaster, dehydrates 2 hours at 550 DEG C.Taking 3.4 kilograms of specific surfaces is 320m ²the fast shedding of aluminium hydroxide and 50 grams of purity of/g, pore volume 0.41ml/g are the calcium oxide of 99%, mix with the aluminum hydroxide solid elastomer after dehydration.

Take the acetic acid 402 grams that purity is 99.5%, dissolved in water, stir, be configured to binding agent.The solid material mixed is placed in bowling machine, the binding agent prepared slowly is sprayed in the solid material mixed, rotate roller forming, obtain catalyst pellet, by bead under the water vapour atmosphere of 100 DEG C slaking 20 hours, 120 DEG C dry 4 hours, 400 DEG C roastings within 3 hours, can catalyst carrier be obtained.Catalyst activity component is potassium oxide, taking 483 grams, potash dissolves in deionized water with 33.6 grams, potassium hydroxide, stir formation stabilizing solution, namely addition constant volume according to carrier obtains activity component impregnation liquid, according to equi-volume impregnating impregnated catalyst, the catalyst of preparation is dried 4 hours, 550 DEG C roastings at 120 DEG C and can be obtained finished catalyst in 3 hours, and obtained specific surface is 338m ²/ g, pore volume 0.38ml/g.

In accordance with the following methods catalyst activity of the present invention is evaluated:

The active evaluation test of catalyst carries out on 10ml sulphur micro-reactor, and the stainless steel tube that reactor is 20mm by internal diameter is made, and reactor is placed in insulating box, and concrete technology flow process is shown in Fig. 2.Loaded catalyst is 10ml (20 ~ 40 order), and the quartz sand of top filling same particle sizes carries out mixing preheating.Adopt H in Japanese Shimadzu GC-2014 gas chromatograph on-line analysis reactor inlet and exit gas ₂s, COS, CO ₂content, constant sulfide analyzed by TCD detector, GDX-301 as carrier, column temperature 120 DEG C, with hydrogen as carrier gas, flow velocity 25ml/min after post; Trace sulfide analyzed by FPD detector, and GDX-301 is as carrier, and column temperature 80 DEG C, does carrier gas with nitrogen, flow velocity 30ml/min after post.

With COS+H ₂o=H ₂s+CO ₂for index reaction, the hydrolyzation catalysis investigating catalyst is active, and inlet gas volume consists of COS 0.03%, CO ₂3%, H ₂o 3%, all the other are N ₂, gas volume air speed is 3000h ^-1, reaction temperature is 60 DEG C, calculates the conversion ratio of COS according to following formula:

$\mathrm{\&eta;}\cos =\frac{M_0-M_1}{M_0}\&times;100\%$

Wherein: M ₀, M ₁represent the volumetric concentration of entrance and exit COS respectively.

Carry out activity rating as stated above to catalyst prepared by embodiment 1 ~ embodiment 7, concrete data are in table 1.

Table 1 catalyst activity contrasts

Claims (5)

1. be applicable to an organic sulfur hydrolyst for natural gas large-scale sulfur recovery device, comprise catalyst carrier and catalyst activity component, it is characterized in that carrier is by Al ₂o ₃with calcium oxide composition, active component is potassium oxide, and catalyst is as follows with the chemical substance of weight parts composition:

Al ₂O ₃78.0～97.9

CaO 0.1～2.0

K ₂O 2.0～20.0

Described carrier is with the fast shedding of aluminium hydroxide for body material, and interpolation aluminum hydroxide solid elastomer and calcium oxide, as modified additive, add appropriate binding agent, adopts roller forming, slaking, drying, roasting, makes; Al in carrier ₂o ₃component is provided by the fast shedding of aluminium hydroxide and aluminum hydroxide solid elastomer, and the two parts by weight ratio is:

The fast shedding of aluminium hydroxide is with Al ₂o ₃meter 100

Aluminum hydroxide solid elastomer is with Al ₂o ₃meter 5.0 ~ 100

CaO in described carrier adds with the form of Paris white or calcium oxide powder;

Described binding agent is any one in acetic acid, nitric acid, citric acid, Alumina gel;

Wherein, the fast shedding specific surface of aluminium hydroxide is greater than 250m ²/ g, pore volume are greater than 0.20ml/g; Aluminum hydroxide solid elastomer specific surface is greater than 350m ²/ g, pore volume are greater than 0.70ml/g;

Described active component K ₂o is with by potash and potassium hydroxide aqueous solution, and the mode be impregnated in catalyst carrier adds, and the mol ratio of potash and potassium hydroxide is 1:1 ~ 5:1.

2. the organic sulfur hydrolyst being applicable to natural gas large-scale sulfur recovery device according to claim 1, is characterized in that carrier is by Al ₂o ₃with calcium oxide composition, active component is potassium oxide, and catalyst is as follows with the chemical substance of weight parts composition:

Al ₂O ₃89.0～95.5

CaO 0.5～1.0

K ₂O 4.0～10.0

Described carrier is with the fast shedding of aluminium hydroxide for body material, and interpolation aluminum hydroxide solid elastomer and calcium oxide, as modified additive, add appropriate binding agent, adopts roller forming, slaking, drying, roasting, makes; Al in carrier ₂o ₃component is provided by the fast shedding of aluminium hydroxide and aluminum hydroxide solid elastomer, and the two parts by weight ratio is:

The fast shedding of aluminium hydroxide is with Al ₂o ₃meter 100

Aluminum hydroxide solid elastomer is with Al ₂o ₃meter 10 ~ 60

Described binding agent is acetic acid;

Wherein, the fast shedding Al of aluminium hydroxide ₂o ₃content>=70%, specific surface is greater than 300m ²/ g, pore volume are greater than 0.35ml/g; Aluminum hydroxide solid elastomer Al ₂o ₃content>=70%, specific surface is greater than 400m ²/ g, pore volume are greater than 0.90ml/g;

Described active component K ₂o is with by potash and potassium hydroxide aqueous solution, and the mode be impregnated in catalyst carrier adds, and the mol ratio of potash and potassium hydroxide is 3:1.

3. the preparation method being applicable to the organic sulfur hydrolyst of natural gas large-scale sulfur recovery device of claim 1, is characterized in that comprising the steps:

1. the preparation of catalyst carrier:

A. aluminum hydroxide solid elastomer dehydrates

The dry glue of raw aluminum hydroxide, under temperature is 450 ~ 650 DEG C of conditions, dehydrates 1 ~ 2 hour, for subsequent use;

B. batch mixing

By the fast shedding of carrier element raw aluminum hydroxide of formula ratio and the aluminum hydroxide solid elastomer dehydrated through step a, calcium oxide mixes, as the support material of Kaolinite Preparation of Catalyst, for subsequent use;

C. the preparation of binder solution A

Mix the amount of material according to step b, take appropriate binding agent, add suitable quantity of water, stir, for subsequent use;

D roller forming

The a part of support material mixed through step b is put into bowling machine, and open bowling machine, spray the binder solution A prepared through step c to the material in bowling machine, material rolls and is shaped to small spheric granules under binder solution A effect; After forming particle, continue to add support material, while interpolation support material, continue spray solution A, until the raw material overwhelming majority is shaped to diameter bead, stop operating, by spheric granules sieve, take out diameter be bead, standby slaking;

E slaking

Steps d is shaping bead, control in the steam atmosphere of 40 ~ 100 DEG C, slaking 10 ~ 40 hours;

F. dry

By through step e slaking bead, control at 80 ~ 160 DEG C of temperature, dry 3 ~ 5 hours;

G. roasting

By through step f drying bead, control at 350 ~ 500 DEG C of temperature, roasting 2 ~ 10 hours, i.e. obtained catalyst carrier;

2. the preparation of catalyst

Catalyst adopts equi-volume impregnating preparation, comprises the steps:

A. the preparation of activity component impregnation liquid

According to following ratio:

Al ₂O ₃78.0～97.9

CaO 0.1～2.0

K ₂O 2.0～20.0

Take potash and potassium hydroxide, the mol ratio controlling potash and potassium hydroxide is 1:1 ~ 5:1; Be dissolved in appropriate amount of deionized water, stir formation stabilizing solution, and namely the addition constant volume according to carrier obtains activity component impregnation liquid, for subsequent use;

B. carrier impregnation

According to equi-volume impregnating, the pre-preg carrier measured is joined in activity component impregnation liquid prepared by step a, flood 10 minutes ~ 3 hours;

C. dry

The carrier flooded by step b, controls 110 ~ 150 DEG C, dries 2 ~ 6 hours;

D. roasting

By carrier dried for step c, control 350 ~ 700 DEG C of roastings 2 ~ 10 hours; The organic sulfur hydrolyst product of natural gas large-scale sulfur recovery device must be applicable to.

4. the preparation method being applicable to the organic sulfur hydrolyst of natural gas large-scale sulfur recovery device of claim 2, is characterized in that comprising the steps:

1. the preparation of catalyst carrier:

A. aluminum hydroxide solid elastomer dehydrates

The dry glue of raw aluminum hydroxide, under temperature is 500 ~ 600 DEG C of conditions, dehydrates 1 ~ 2 hour, for subsequent use;

B. batch mixing

By the fast shedding of carrier element raw aluminum hydroxide of formula ratio and the aluminum hydroxide solid elastomer dehydrated through step a, calcium oxide mixes, as the support material of Kaolinite Preparation of Catalyst, for subsequent use;

C. the preparation of binder solution A

Mix the amount of material according to step b, take appropriate binding agent, add suitable quantity of water, stir, for subsequent use;

D roller forming

The a part of support material mixed through step b is put into bowling machine, and open bowling machine, spray the binder solution A prepared through step c to the material in bowling machine, material rolls and is shaped to small spheric granules under binder solution A effect; After forming particle, continue to add support material, while interpolation support material, continue spray solution A, until the raw material overwhelming majority is shaped to diameter bead, stop operating, by spheric granules sieve, take out diameter be bead, standby slaking;

E slaking

Steps d is shaping bead, control in the steam atmosphere of 80 ~ 100 DEG C, slaking 10 ~ 40 hours;

F. dry

By through step e slaking bead, control at 110 ~ 130 DEG C of temperature, dry 3 ~ 5 hours;

G. roasting

By through step f drying bead, control at 380 ~ 450 DEG C of temperature, roasting 3 ~ 5 hours, i.e. obtained catalyst carrier;

2. the preparation of catalyst

Catalyst adopts equi-volume impregnating preparation, comprises the steps:

A. the preparation of activity component impregnation liquid

According to following ratio:

Al ₂O ₃89.0～95.5

CaO 0.5～1.0

K ₂O 4.0～10.0

Take potash and potassium hydroxide, the mol ratio controlling potash and potassium hydroxide is 3:1; Be dissolved in appropriate amount of deionized water, stir formation stabilizing solution, and namely the addition constant volume according to carrier obtains activity component impregnation liquid, for subsequent use;

B. carrier impregnation

According to equi-volume impregnating, the pre-preg carrier measured is joined in activity component impregnation liquid prepared by step a, flood 10 minutes ~ 3 hours;

C. dry

The carrier flooded by step b, controls 110 ~ 150 DEG C, dries 2 ~ 6 hours;

D. roasting

By carrier dried for step c, control 500 ~ 600 DEG C of roastings 2 ~ 10 hours; The organic sulfur hydrolyst product of natural gas large-scale sulfur recovery device must be applicable to.

5. the application being applicable to the organic sulfur hydrolyst of natural gas large-scale sulfur recovery device of claim 1, is characterized in that the tempreture organic sulphur hydrolysis process being applicable to natural gas large-scale sulfur recovery device.