CN103480355A - Organic sulfur hydrolysis catalyst applicable to natural gas large-scale sulfur recovery device and preparation method thereof - Google Patents
Organic sulfur hydrolysis catalyst applicable to natural gas large-scale sulfur recovery device and preparation method thereof Download PDFInfo
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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
Technical field
The present invention is a kind of organic sulfur hydrolyst that is applicable to the large-scale sulfur recovery unit of natural gas and preparation method thereof.Belong to the method that adopts catalysis process to remove sulphur compound in mist.
Background technology
The ratio of natural gas in world's primary energy consumption structure reached 25% left and right, and surpassing coal becomes second, has become a kind of important energy sources.At present, in gas purifying process, sulfur recovery facility mainly adopts the techniques 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, as increasing as the scale of sulfur recovery facility, it is developing direction from now on that sulfur recovery facility maximizes.Because, can reduce operating cost, 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 is greatly developing gas industry, and some new high-sulfur Large gas fields are developed in succession, and this has just proposed new demand to gas purifying process.At present, the general phosgene of Zhongyuan Oil Field branch company of China Petrochemical Industry field Gas Purification Factory is the gas purification plant of China's maximum, and this factory has the sulfur recovery facility that 12 cover list cover scales are 200kt/a, and device adopts U.S. Black& The technique bag of Veatch company, matching used catalyst is import, and the import catalyst is expensive, changes a catalyst cost huge.
Because organic sulfur content in natural gas is higher, organic sulfur hydrolysis unit generally is set separately before the Crouse unit.For example, the general smooth Gas Purification Factory of China Petrochemical Industry just arranges the organic sulfur hydrolysis unit in the sulfur recovery unit front portion, in order to reduce the content of organic sulfur in natural gas.Owing to containing a certain amount of carbon dioxide in natural gas, the existence of carbon dioxide has certain inhibitory action to the hydrolysis of organic sulfur, this just requires to compare other devices in the catalytic activity of the organic sulfur hydrolyst of natural-gas sulphur retracting device use and wants high, otherwise can't meet the requirement of device.Both at home and abroad, the organic sulfur hydrolyst that large-scale sulfur recovery unit is used is generally the PURASPEC-2312 catalyst that ten thousand rich (Johnson Matthey) company is believed in the Britain village, this catalyst be take aluminium oxide as main component, have the advantages that specific area is large, hydrolysis effect is good, but the low temperature hydrolysis activity is slightly poor.At present, the catalyst that exploitation has good low temperature tempreture organic sulphur hydrolysis activity, the requirement that meets large-scale natural gas field sulfur recovery unit is the developing direction of such catalyst.
CN00119385.6 has introduced a kind of hydrolytic catalyst of carbonyl sulfur, and it consists of γ-Al
2o
383%～97%, K
2o 2%～15%, and BaO 0.1%～2%.This catalyst is to adopt the equal-volume solution dipping method to be prepared, and its purposes is 80～150 ℃ of temperature, normal pressure, and COS content is less than 800mg/m
3, air speed 6000～9000h
-1carry out desulfurization under condition.The catalyst serviceability temperature of this patented invention is higher, generally, more than 80 ℃, can not meet the low temperature instructions for use.
CN201010556207.9 has introduced a kind of for removing the catalyst of Chemical Manufacture unstripped gas cos, 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 the magnesium-aluminum-based hydrotalcite, add water and mediate, extruded moulding, drying, roasting, make the 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 that is applicable at present the large-scale sulfur recovery unit of natural gas 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 a kind of organic sulfur hydrolyst for the large-scale sulfur recovery unit of natural gas that specific surface is large, pore volume large, low temperature tempreture organic sulphur hydrolysis activity is high that has is provided.In order to solve, adopt large-scale sulfur recovery unit to process in natural gas, the problem that the organic sulfur content run into is higher, meet the quality requirement that natural gas dispatches from the factory.
The present invention also aims to provide the preparation method of the organic sulfur hydrolyst that is applicable to the large-scale sulfur recovery unit of natural gas that a kind of preparation cost is lower.
Purpose of the present invention can reach by following measure:
The organic sulfur hydrolyst that is applicable to the large-scale sulfur recovery unit of natural gas of the present invention, comprise catalyst carrier and catalyst activity component, it is characterized in that carrier is by Al
2o
3with calcium oxide, form, active component is potassium oxide, and catalyst forms as follows in the chemical substance of parts by weight:
Al
2O
3 78.0～97.9
CaO 0.1～2.0
K
2O 2.0～20.0
It is body material that described carrier be take the fast shedding of aluminium hydroxide, adds aluminum hydroxide solid elastomer and calcium oxide as modified additive, adds 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, aluminium colloidal sol;
Wherein, the fast shedding specific surface of aluminium hydroxide is greater than 250m
2/ g, pore volume are greater than 0.20ml/g; The 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 on 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 existence of carbon dioxide has certain inhibitory action to the hydrolysis of organic sulfur, and this compares and want high with regard to the catalyst activity that requires gas plant to use.The present invention is characterized in that catalyst carrier usings the fast shedding of aluminium hydroxide as raw material, adds aluminum hydroxide solid elastomer and calcium oxide to be prepared from as auxiliary agent simultaneously, in order to improve the hydrolysing activity of catalyst.What the active constituent of catalyst was used be the alkali metal that alkalescence is stronger, and catalyst prepared by the present invention has that specific surface is large, pore volume is 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, have guaranteed 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%, make organic sulfur content in natural gas significantly descend.Therefore, this catalyst can meet the specification requirement of the sulfur recovery unit of natural gas purification industry.
Purpose of the present invention can also reach by following measure:
The of the present invention organic sulfur hydrolyst that is applicable to the large-scale sulfur recovery unit of natural gas, is characterized in that carrier is by Al
2o
3with calcium oxide, form, active component is potassium oxide, and catalyst forms as follows in the chemical substance of parts by weight:
Al
2O
3 9.0～95.5
CaO 0.5～1.0
K
2O 4.0～10.0
It is body material that described carrier be take the fast shedding of aluminium hydroxide, adds aluminum hydroxide solid elastomer and calcium oxide as modified additive, adds 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 on catalyst carrier adds, and the mol ratio of potash and potassium hydroxide is 3:1.
It is preferred technical scheme.
The preparation method who is applicable to the organic sulfur hydrolyst of the large-scale sulfur recovery unit of natural gas 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 is under 450～650 ℃ of conditions in temperature, dehydrates 1～2 hour, standby;
B. batch mixing
By the fast shedding of the 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, standby;
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, standby;
The d roller forming
A part of raw material that will mix through step b is put into bowling machine, opens bowling machine, and the material in bowling machine sprays the binder solution A prepared through step c, and material rolls and is shaped to small spheric granules under binder solution A effect; After forming particle, continue to add raw material, continue spray solution A when adding raw material, until the raw material overwhelming majority is shaped to diameter
bead, stop operating.By the spheric granules screening, the taking-up diameter is
bead, standby slaking;
The e slaking
By the steps d moulding
bead, be controlled in the steam atmosphere of 40～100 ℃ slaking 10～40 hours;
F. dry
Will be through step e slaking
bead, be controlled at 80～160 ℃ of temperature dry 3～5 hours;
G. roasting
Will be through step f drying
bead, be controlled at 350～500 ℃ of temperature, roasting 2～10 hours, make catalyst carrier.
2. the preparation of catalyst
Catalyst adopts the equi-volume impregnating preparation, comprises the steps:
A. the preparation of activity component impregnation liquid
According to following ratio:
Al
2O
3 78.0～97.9
CaO 0.1～2.0
K
2O 2.0～20.0
Take potash and potassium hydroxide, the mol ratio of controlling potash and potassium hydroxide is 1:1～5:1; Be dissolved in appropriate amount of deionized water, the formation stabilizing solution that stirs, obtain activity component impregnation liquid according to the addition constant volume of carrier, standby;
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 that step b has been flooded, control 110～150 ℃, dries 2～6 hours;
D. roasting
The dried carrier by step c, control 350～700 ℃ of roastings 2～10 hours; Must be applicable to the organic sulfur hydrolyst product of the large-scale sulfur recovery unit of natural gas.
The present inventor is applicable to the inventive concept of the organic sulfur hydrolyst component of the large-scale sulfur recovery unit of natural gas according to development, well-designed that with formula, be complementary, easy to operate, lower-cost preparation method, thereby completed task of the present invention, obtained beyond thought technique effect.
The preparation method who is applicable to the organic sulfur hydrolyst of the large-scale sulfur recovery unit of natural gas of the present invention, comprise the steps:
1. the preparation of catalyst carrier:
A. aluminum hydroxide solid elastomer dehydrates
The dry glue of raw aluminum hydroxide is under 500～600 ℃ of conditions in temperature, dehydrates 1～2 hour, standby;
B. batch mixing
By the fast shedding of the 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, standby;
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, standby;
The d roller forming
A part of raw material that will mix through step b is put into bowling machine, opens bowling machine, and the material in bowling machine sprays the binder solution A prepared through step c, and material rolls and is shaped to small spheric granules under binder solution A effect; After forming particle, continue to add raw material, continue spray solution A when adding raw material, until the raw material overwhelming majority is shaped to diameter
bead, stop operating.By the spheric granules screening, the taking-up diameter is
bead, standby slaking;
The e slaking
By the steps d moulding
bead, be controlled in the steam atmosphere of 80～100 ℃ slaking 10～40 hours;
F. dry
Will be through step e slaking
bead, be controlled at 110～130 ℃ of temperature dry 3～5 hours;
G. roasting
Will be through step f drying
bead, be controlled at 380～450 ℃ of temperature, roasting 3～5 hours, make catalyst carrier.
2. the preparation of catalyst
Catalyst adopts the equi-volume impregnating preparation, comprises the steps:
A. the preparation of activity component impregnation liquid
According to following ratio:
Al
2O
3 89.0～95.5
CaO 0.5～1.0
K
2O 4.0～10.0
Take potash and potassium hydroxide, the mol ratio of controlling potash and potassium hydroxide is 3:1; Be dissolved in appropriate amount of deionized water, the formation stabilizing solution that stirs, obtain activity component impregnation liquid according to the addition constant volume of carrier, standby;
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 that step b has been flooded, control 110～150 ℃, dries 2～6 hours;
D. roasting
The dried carrier by step c, control 500～600 ℃ of roastings 2～10 hours; Must be applicable to the organic sulfur hydrolyst product of the large-scale sulfur recovery unit of natural gas.
It is the disclosed preferred technical scheme of inventor.
The application that is applicable to the organic sulfur hydrolyst of the large-scale sulfur recovery unit of natural gas of the present invention, is characterized in that being applicable to the tempreture organic sulphur hydrolysis process of the large-scale sulfur recovery unit of natural gas.
Organic sulfur hydrolyst that is applicable to the large-scale sulfur recovery unit of natural gas of the present invention and preparation method thereof has following good effect compared to existing technology:
1. a kind of organic sulfur hydrolyst for the large-scale sulfur recovery unit of natural gas that specific surface is large, pore volume large, low temperature tempreture organic sulphur hydrolysis activity is high that has is provided.
2. a kind of easy to operate, lower-cost preparation method who is applicable to the organic sulfur hydrolyst of the large-scale sulfur recovery unit of natural gas is provided.
3. the specific surface of catalyst of the present invention is greater than 300m
2/ g, pore volume are greater than 0.35ml/g, have guaranteed 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%, make organic sulfur content in natural gas significantly descend.Therefore, this catalyst can meet the specification requirement of the sulfur recovery unit of natural gas purification industry.
4. catalyst of the present invention can meet the specification requirement of the removal of sulfur compounds of the large-scale sulfur recovery unit of natural gas purification industry.And guaranteed the technical indicator that gas product is up to state standards and stipulates.
The accompanying drawing explanation
Fig. 1 is catalyst preparation flow schematic diagram of the present invention
Fig. 2 is laboratory catalyst activity evaluating apparatus schematic flow sheet
In figure:
The 1-CO2 gas cylinder, 2-COS gas cylinder, 3-N
2gas cylinder, the 4-water bottle, the 5-mass flowmenter, the 6-pump, the 7-reactor, 8-amasss sulphur device, 9-cold-trap, 10-caustic treater, 11-chromatogram, the emptying of 12-tail gas.
The specific embodiment
The present invention will now be further detailed embodiment:
Taking specific surface is 422m
21 kilogram of the aluminum hydroxide solid elastomer of/g, pore volume 1.10ml/g is positioned in roaster, dehydrates 2 hours under 550 ℃.Taking 4 kilograms of specific surfaces is 320m
2the calcium oxide that the fast shedding of the aluminium hydroxide of/g, pore volume 0.41ml/g and 50 gram purity are 99%, mix with the aluminum hydroxide solid elastomer after dehydration.
Acetic acid 402 grams that to take purity be 99.5%, dissolve in it in water, stirs, and is configured to binding agent.The solid material mixed is placed in to bowling machine, the binding agent prepared is slowly sprayed in the solid material mixed, rotate roller forming, obtain
catalyst pellet, bead 20 hours, 120 ℃ of slakings under the water vapour atmosphere of 100 ℃ are dried to 4 hours, 400 ℃ roastings and within 3 hours, can make catalyst carrier.The catalyst activity component is potassium oxide, take potash 483 grams and potassium hydroxide 33.6 grams dissolve in deionized water, the formation stabilizing solution stirs, obtain activity component impregnation liquid according to the addition constant volume of carrier, according to the equi-volume impregnating impregnated catalyst, the catalyst of preparation is dried 4 hours, 550 ℃ roastings at 120 ℃ can make the catalyst finished product in 3 hours, and the specific surface made is 321m
2/ g, pore volume 0.37ml/g.
Taking specific surface is 422m
21 kilogram of the aluminum hydroxide solid elastomer of/g, pore volume 1.10ml/g is positioned in roaster, dehydrates 2 hours under 550 ℃.Taking 5 kilograms of specific surfaces is 320m
2the calcium oxide that the fast shedding of the aluminium hydroxide of/g, pore volume 0.41ml/g and 60 gram purity are 99%, mix with the aluminum hydroxide solid elastomer after dehydration.
Acetic acid 402 grams that to take purity be 99.5%, dissolve in it in water, stirs, and is configured to binding agent.The solid material mixed is placed in to bowling machine, the binding agent prepared is slowly sprayed in the solid material mixed, rotate roller forming, obtain
catalyst pellet, bead 20 hours, 120 ℃ of slakings under the water vapour atmosphere of 100 ℃ are dried to 4 hours, 400 ℃ roastings and within 3 hours, can make catalyst carrier.The catalyst activity component is potassium oxide, take potash 483 grams and potassium hydroxide 33.6 grams dissolve in deionized water, the formation stabilizing solution stirs, obtain activity component impregnation liquid according to the addition constant volume of carrier, according to the equi-volume impregnating impregnated catalyst, the catalyst of preparation is dried 4 hours, 550 ℃ roastings at 120 ℃ can make the catalyst finished product in 3 hours, and the specific surface made is 315m
2/ g, pore volume 0.36ml/g.
Taking specific surface is 422m
21 kilogram of the aluminum hydroxide solid elastomer of/g, pore volume 1.10ml/g is positioned in roaster, dehydrates 2 hours under 550 ℃.Taking 4 kilograms of specific surfaces is 320m
2the calcium oxide that the fast shedding of the aluminium hydroxide of/g, pore volume 0.41ml/g and 50 gram purity are 99%, mix with the aluminum hydroxide solid elastomer after dehydration.
Acetic acid 402 grams that to take purity be 99.5%, dissolve in it in water, stirs, and is configured to binding agent.The solid material mixed is placed in to bowling machine, the binding agent prepared is slowly sprayed in the solid material mixed, rotate roller forming, obtain
catalyst pellet, bead 20 hours, 120 ℃ of slakings under the water vapour atmosphere of 100 ℃ are dried to 4 hours, 400 ℃ roastings and within 3 hours, can make catalyst carrier.The catalyst activity component is potassium oxide, take potash 511 grams and potassium hydroxide 22.4 grams dissolve in deionized water, the formation stabilizing solution stirs, obtain activity component impregnation liquid according to the addition constant volume of carrier, according to the equi-volume impregnating impregnated catalyst, the catalyst of preparation is dried 4 hours, 550 ℃ roastings at 120 ℃ can make the catalyst finished product in 3 hours, and the specific surface made is 323m
2/ g, pore volume 0.37ml/g.
Taking specific surface is 422m
21 kilogram of the aluminum hydroxide solid elastomer of/g, pore volume 1.10ml/g is positioned in roaster, dehydrates 2 hours under 550 ℃.Taking 4 kilograms of specific surfaces is 320m
2the calcium oxide that the fast shedding of the aluminium hydroxide of/g, pore volume 0.41ml/g and 50 gram purity are 99%, mix with the aluminum hydroxide solid elastomer after dehydration.
Acetic acid 402 grams that to take purity be 99.5%, dissolve in it in water, stirs, and is configured to binding agent.The solid material mixed is placed in to bowling machine, the binding agent prepared is slowly sprayed in the solid material mixed, rotate roller forming, obtain
catalyst pellet, bead 20 hours, 120 ℃ of slakings under the water vapour atmosphere of 100 ℃ are dried to 4 hours, 400 ℃ roastings and within 3 hours, can make catalyst carrier.The catalyst activity component is potassium oxide, take potash 552 grams and potassium hydroxide 37.5 grams dissolve in deionized water, the formation stabilizing solution stirs, obtain activity component impregnation liquid according to the addition constant volume of carrier, according to the equi-volume impregnating impregnated catalyst, the catalyst of preparation is dried 4 hours, 550 ℃ roastings at 120 ℃ can make the catalyst finished product in 3 hours, and the specific surface made is 317m
2/ g, pore volume 0.37ml/g.
Taking specific surface is 422m
21 kilogram of the aluminum hydroxide solid elastomer of/g, pore volume 1.10ml/g is positioned in roaster, dehydrates 2 hours under 550 ℃.Taking 4 kilograms of specific surfaces is 320m
2the calcium oxide that the fast shedding of the aluminium hydroxide of/g, pore volume 0.41ml/g and 50 gram purity are 99%, mix with the aluminum hydroxide solid elastomer after dehydration.
Acetic acid 402 grams that to take purity be 99.5%, dissolve in it in water, stirs, and is configured to binding agent.The solid material mixed is placed in to bowling machine, the binding agent prepared is slowly sprayed in the solid material mixed, rotate roller forming, obtain
catalyst pellet, bead 20 hours, 120 ℃ of slakings under the water vapour atmosphere of 100 ℃ are dried to 4 hours, 400 ℃ roastings and within 3 hours, can make catalyst carrier.The catalyst activity component is potassium oxide, take potash 270 grams and potassium hydroxide 18 grams dissolve in deionized water, the formation stabilizing solution stirs, obtain activity component impregnation liquid according to the addition constant volume of carrier, according to the equi-volume impregnating impregnated catalyst, the catalyst of preparation is dried 4 hours, 550 ℃ roastings at 120 ℃ can make the catalyst finished product in 3 hours, and the specific surface made is 326m
2/ g, pore volume 0.37ml/g.
Taking specific surface is 422m
20.6 kilogram of the aluminum hydroxide solid elastomer of/g, pore volume 1.10ml/g is positioned in roaster, dehydrates 2 hours under 550 ℃.Taking 4.4 kilograms of specific surfaces is 320m
2the calcium oxide that the fast shedding of the aluminium hydroxide of/g, pore volume 0.41ml/g and 50 gram purity are 99%, mix with the aluminum hydroxide solid elastomer after dehydration.
Acetic acid 402 grams that to take purity be 99.5%, dissolve in it in water, stirs, and is configured to binding agent.The solid material mixed is placed in to bowling machine, the binding agent prepared is slowly sprayed in the solid material mixed, rotate roller forming, obtain
catalyst pellet, bead 20 hours, 120 ℃ of slakings under the water vapour atmosphere of 100 ℃ are dried to 4 hours, 400 ℃ roastings and within 3 hours, can make catalyst carrier.The catalyst activity component is potassium oxide, take potash 483 grams and potassium hydroxide 33.6 grams dissolve in deionized water, the formation stabilizing solution stirs, obtain activity component impregnation liquid according to the addition constant volume of carrier, according to the equi-volume impregnating impregnated catalyst, the catalyst of preparation is dried 4 hours, 550 ℃ roastings at 120 ℃ can make the catalyst finished product in 3 hours, and the specific surface made is 309m
2/ g, pore volume 0.35ml/g.
Embodiment 7
Taking specific surface is 422m
21.6 kilograms of the aluminum hydroxide solid elastomers of/g, pore volume 1.10ml/g are positioned in roaster, dehydrate 2 hours under 550 ℃.Taking 3.4 kilograms of specific surfaces is 320m
2the calcium oxide that the fast shedding of the aluminium hydroxide of/g, pore volume 0.41ml/g and 50 gram purity are 99%, mix with the aluminum hydroxide solid elastomer after dehydration.
Acetic acid 402 grams that to take purity be 99.5%, dissolve in it in water, stirs, and is configured to binding agent.The solid material mixed is placed in to bowling machine, the binding agent prepared is slowly sprayed in the solid material mixed, rotate roller forming, obtain
catalyst pellet, bead 20 hours, 120 ℃ of slakings under the water vapour atmosphere of 100 ℃ are dried to 4 hours, 400 ℃ roastings and within 3 hours, can make catalyst carrier.The catalyst activity component is potassium oxide, take potash 483 grams and potassium hydroxide 33.6 grams dissolve in deionized water, the formation stabilizing solution stirs, obtain activity component impregnation liquid according to the addition constant volume of carrier, according to the equi-volume impregnating impregnated catalyst, the catalyst of preparation is dried 4 hours, 550 ℃ roastings at 120 ℃ can make the catalyst finished product in 3 hours, and the specific surface made is 338m
2/ g, pore volume 0.38ml/g.
In accordance with the following methods catalyst activity of the present invention is estimated:
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 the concrete technology flow process is shown in Fig. 2.Loaded catalyst is 10ml (20～40 order), the quartz sand mixing preheating of top filling same particle sizes.Adopt H in Japanese Shimadzu GC-2014 gas chromatograph on-line analysis reactor inlet and exit gas
2s, COS, CO
2content, the TCD detector is analyzed constant sulfide, GDX-301 is as carrier, 120 ℃ of column temperatures, do carrier gas with hydrogen, flow velocity 25ml/min after post; The FPD detector is analyzed trace sulfide, and GDX-301 is as carrier, and 80 ℃ of column temperatures, do carrier gas with nitrogen, flow velocity 30ml/min after post.
With COS+H
2o=H
2s+CO
2for the index reaction, investigate the hydrolyzation catalysis activity of catalyst, the inlet gas volume consists of COS 0.03%, CO
23%, H
2o 3%, and all the other are N
2, the gas volume air speed is 3000h
-1, reaction temperature is 60 ℃, calculates the conversion ratio of COS according to following formula:
Wherein: M
0, M
1represent respectively the volumetric concentration of entrance and exit COS.
Catalyst to embodiment 1～embodiment 7 preparations carries out activity rating as stated above, and concrete data are in Table 1.
The contrast of table 1 catalyst activity
Claims (5)
1. an organic sulfur hydrolyst that is applicable to the large-scale sulfur recovery unit of natural gas, comprise catalyst carrier and catalyst activity component, it is characterized in that carrier is by Al
2o
3with calcium oxide, form, active component is potassium oxide, and catalyst forms as follows in the chemical substance of parts by weight:
Al
2O
3 78.0～97.9
CaO 0.1～2.0
K
2O 2.0～20.0
It is body material that described carrier be take the fast shedding of aluminium hydroxide, adds aluminum hydroxide solid elastomer and calcium oxide as modified additive, adds 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, aluminium colloidal sol;
Wherein, the fast shedding specific surface of aluminium hydroxide is greater than 250m
2/ g, pore volume are greater than 0.20ml/g; The 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 on catalyst carrier adds, and the mol ratio of potash and potassium hydroxide is 1:1～5:1.
2. according to the organic sulfur hydrolyst that is applicable to the large-scale sulfur recovery unit of natural gas of claim 1, it is characterized in that carrier is by Al
2o
3with calcium oxide, form, active component is potassium oxide, and catalyst forms as follows in the chemical substance of parts by weight:
Al
2O
3 89.0～95.5
CaO 0.5～1.0
K
2O 4.0～10.0
It is body material that described carrier be take the fast shedding of aluminium hydroxide, adds aluminum hydroxide solid elastomer and calcium oxide as modified additive, adds 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 on catalyst carrier adds, and the mol ratio of potash and potassium hydroxide is 3:1.
3. the preparation method of the organic sulfur hydrolyst that is applicable to the large-scale sulfur recovery unit of natural gas of a 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 is under 450～650 ℃ of conditions in temperature, dehydrates 1～2 hour, standby;
B. batch mixing
By the fast shedding of the 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, standby;
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, standby;
The d roller forming
A part of raw material that will mix through step b is put into bowling machine, opens bowling machine, and the material in bowling machine sprays the binder solution A prepared through step c, and material rolls and is shaped to small spheric granules under binder solution A effect; After forming particle, continue to add raw material, continue spray solution A when adding raw material, until the raw material overwhelming majority is shaped to diameter
bead, stop operating.By the spheric granules screening, the taking-up diameter is
bead, standby slaking;
The e slaking
By the steps d moulding
bead, be controlled in the steam atmosphere of 40～100 ℃ slaking 10～40 hours;
F. dry
Will be through step e slaking
bead, be controlled at 80～160 ℃ of temperature dry 3～5 hours;
G. roasting
Will be through step f drying
bead, be controlled at 350～500 ℃ of temperature, roasting 2～10 hours, make catalyst carrier.
2. the preparation of catalyst
Catalyst adopts the equi-volume impregnating preparation, comprises the steps:
A. the preparation of activity component impregnation liquid
According to following ratio:
Al
2O
3 78.0～97.9
CaO 0.1～2.0
K
2O 2.0～20.0
Take potash and potassium hydroxide, the mol ratio of controlling potash and potassium hydroxide is 1:1～5:1; Be dissolved in appropriate amount of deionized water, the formation stabilizing solution that stirs, obtain activity component impregnation liquid according to the addition constant volume of carrier, standby;
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 that step b has been flooded, control 110～150 ℃, dries 2～6 hours;
D. roasting
The dried carrier by step c, control 350～700 ℃ of roastings 2～10 hours; Must be applicable to the organic sulfur hydrolyst product of the large-scale sulfur recovery unit of natural gas.
4. the preparation method of the organic sulfur hydrolyst that is applicable to the large-scale sulfur recovery unit of natural gas of a 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 is under 500～600 ℃ of conditions in temperature, dehydrates 1～2 hour, standby;
B. batch mixing
By the fast shedding of the 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, standby;
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, standby;
The d roller forming
A part of raw material that will mix through step b is put into bowling machine, opens bowling machine, and the material in bowling machine sprays the binder solution A prepared through step c, and material rolls and is shaped to small spheric granules under binder solution A effect; After forming particle, continue to add raw material, continue spray solution A when adding raw material, until the raw material overwhelming majority is shaped to diameter
bead, stop operating.By the spheric granules screening, the taking-up diameter is
bead, standby slaking;
The e slaking
By the steps d moulding
bead, be controlled in the steam atmosphere of 80～100 ℃ slaking 10～40 hours;
F. dry
Will be through step e slaking
bead, be controlled at 110～130 ℃ of temperature dry 3～5 hours;
G. roasting
Will be through step f drying
bead, be controlled at 380～450 ℃ of temperature, roasting 3～5 hours, make catalyst carrier.
2. the preparation of catalyst
Catalyst adopts the equi-volume impregnating preparation, comprises the steps:
A. the preparation of activity component impregnation liquid
According to following ratio:
Al
2O
3 89.0～95.5
CaO 0.5～1.0
K
2O 4.0～10.0
Take potash and potassium hydroxide, the mol ratio of controlling potash and potassium hydroxide is 3:1; Be dissolved in appropriate amount of deionized water, the formation stabilizing solution that stirs, obtain activity component impregnation liquid according to the addition constant volume of carrier, standby;
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 that step b has been flooded, control 110～150 ℃, dries 2～6 hours;
D. roasting
The dried carrier by step c, control 500～600 ℃ of roastings 2～10 hours; Must be applicable to the organic sulfur hydrolyst product of the large-scale sulfur recovery unit of natural gas.
5. the application of the organic sulfur hydrolyst that is applicable to the large-scale sulfur recovery unit of natural gas of claim 1, is characterized in that being applicable to the tempreture organic sulphur hydrolysis process of the large-scale sulfur recovery unit of natural gas.
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| CN108367237A (en) * | 2015-08-06 | 2018-08-03 | 氟石科技公司 | Improve the system and method that sulphur is recycled from Claus process tail gases |
| CN108970618A (en) * | 2017-05-31 | 2018-12-11 | 中国石油化工股份有限公司 | Catalyst for recovering sulfur and preparation method thereof |
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| CN117398985A (en) * | 2023-10-19 | 2024-01-16 | 北京铝能清新环境技术有限公司 | Active alumina carrier sphere in hydrolysis catalyst and preparation method thereof |
| CN117398985B (en) * | 2023-10-19 | 2024-05-24 | 北京铝能清新环境技术有限公司 | Active alumina carrier sphere in hydrolysis catalyst and preparation method thereof |
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