CN100363100C - Desulfur catalyst - Google Patents

Abstract

The present invention discloses a solid desulfurization catalyst which is used for eliminating sulfide, sulfur oxide, thioether and other toxic and harmful substances in natural gas and flue gas at a certain temperature and under a certain pressure. The present invention contains the following components of the percentage by weight adopting the catalyst weight as the reference: 6.5% to 65% of ZnO, 0.5% to 2% of NiO, 11% to 40% of CaAlO3, 0.5% to 2% of TiO2, 0.9% to 2% of C0O, 0.7% to 3% of M0O and 20% to 70% of Al2O3. The present invention can be used for eliminating sulfide, sulfur oxide, thioether and other toxic and harmful substances in natural gas and flue gas; the present invention is capable of eliminating organic sulfur, inorganic sulphur, sulphur of the ppm level content, sulphur with the sulfur content of 80 milligram per cubic metre, sulphur at normal temperatures and sulphur at the temperature of 400 DEG C to 500 DEG C; when the present invention is used in a large sized synthetic ammonia installation of 300 thousands of tons, both organic sulfur and inorganic sulphur in natural gas can be removed; when the present invention is used for large-sized power generating plants adopting coal as fuel, SO2 in exhaust flue gas can be removed.

Description

Desulphurization catalyst

Technical field

The present invention relates to a kind ofly under certain temperature, pressure condition, to remove in the natural gas, the solid desulphurization catalyst of poisonous and harmful substance such as the sulfide in the flue gas, oxysulfide, thioether, specifically, the present invention relates to a kind of zinc solid desulphurization catalyst that contains.

Background technology

Industries such as the energy, chemical industry, metallurgy, electronics use the SO that contains in the flue gas that fossil fuel (coal, oil, natural gas etc.) discharged ₂Atmosphere is caused severe contamination, and China has become SO in the world at present ₂Discharge first big country, the third-largest acid rain district, environmental problem has become the key issue that can Chinese national economy develop.Industrial practice in recent years shows that flue gases purification is control SO ₂The effective way of discharging, desulphurization catalyst is the pith of flue gases purification, it can be divided into solid and liquid desulphurization catalyst, wherein, zinc oxide solid desulphurization catalyst is at various petrochemical materials gas, being most widely used in the smart desulfurization of industry gas, Zinc oxide desulfurizer mainly contains two kinds of high temperature and low forms, the former serviceability temperature is 350-400 ℃, latter's serviceability temperature is 180-250 ℃, because two types desulfurizing agent all needs to use at a certain temperature, needs thermal source, and consumes certain energy, generally all can not use at normal temperatures, therefore the scope of application of this catalyst is narrower;

For many years, the Soviet Union is just with zinc ore masonry desulphurization catalyst, but bad desulfurization effects, the negative resistance that adds that causes to system increases; The more existing producers of China make desulphurization catalyst with the oxide of zinc, salt etc. with other chemical substance, as Patent Office of the People's Republic of China with 85103555 disclosed a kind of " iron-manganese-zinc desulfurizing agent for gaseous hydrocarbons ", it is very satisfied that its desulfurized effect does not make us yet, reason has: a, can not remove the sulfide of high-load in the discharging gas that natural gas and coal produce, it requires the content of sulphur in the unstripped gas must be lower than 0.5ppm, when every cubic metre of sulfur content in the natural gas reached the milligram level, catalyst poisoning will appear; B, the used regeneration gas of this desulphurization catalyst regeneration are H ₂And C ₀Etc. expensive gases, the regeneration expense is very expensive; Though c, this desulphurization catalyst can be regenerated, need ability regeneration in 350 ℃ of following 10-12 hours, and its activity also descends to some extent.

Summary of the invention

The objective of the invention is to overcome the shortcoming of above-mentioned prior art and provide a kind of and can the sulfide of high-load in the discharging gas be adsorbed, can regenerate and the recovery time is short, active high, and the solid desulphurization catalyst that can use under high and low and normal temperature in regeneration back.

The object of the present invention is achieved like this:

Nickel series conversion catalyzer has the above-mentioned various deficiencies of appearance of the desulphurization catalyst of special responsive characteristics and prior art to sulfide by analysis, and the present inventor has been found that on zinc is the basis of desulphurization catalyst prescription and adds an amount of NiO, TiO ₂, Al ₂O ₃Deng, be effectively to the purpose that reaches foregoing invention, be successful based on the present invention of this discovery.

In other words, containing zinc solid desulphurization catalyst according to the invention provides an energy to what the sulfide of high-load in the discharging gas adsorbed, is benchmark with the catalyst weight, contains the component of following percentage by weight:

ZnO..................6.5% to 65%

NiO...................0.5% to 2%

CaAlO ₃... ... ... .11% to 40%

TiO ₂... ... ... 0.5% to 2%

CoO...................0.9% to 2%

MoO...................0.7% to 3%

Al ₂O ₃... ... ... ..20% to 70%

The average pore size of this catalyst is 16.1nm, and pore volume is 0.5～1.6ml/g; Specific area is 309～501m ²/ g, bulk density is 1.08g/ml, compression strength is 〉=150N/cm.

The Ni that is used for NiO of the present invention has great suction-operated to sulfide, can both be removed by its collection less than 10 other sulfide of ppm level, can be used for purified natural gas and is the waste gas that fuel is discharged with the coal, and NiO aims to remove H ₂S adds;

Be used for Al of the present invention ₂O ₃Itself have hole rate preferably, and should be to have active Al ₂O ₃, the reason that adds it is in order to adsorb SO ₂

Be used for TiO of the present invention ₂Have mercaptan, thioether and sulfosalt are had suction-operated, and the alkene in the natural gas is also had suction-operated, because in the prescription Al is arranged ₂O ₃, TiO ₂Adding protection NiO component is also had effect, prevent itself and Al ₂O ₃React and generate NiAl ₂O ₄Thereby influence its activity;

The ZnO that is used for the present invention can be to the most of H in the natural gas ₂S removes;

The Ca that is used for the present invention adds with the form of pure calcium aluminate, and it can improve the intensity of catalyst;

The effect and the TiO that are used for the present invention's Mo, Co ₂Similar, but they can not be to Al ₂O ₃Play a protective role.

Production method of the present invention is as follows: the each component raw material in the above-mentioned prescription is mixed the back grinding in ball grinder 4～6 hours by the amount described in the prescription, be ground to the above fineness of 120 orders and must account for 30% of weight, after tablet machine is beaten sheet, crusher in crushing (being granulation) then, send into compression moulding in the ring squeezer after crossing 120 purposes sieve, again at 4kg/cm ²Still kettle in steam the roasting temperature of delivering to 400～500 ℃ of stove inherences after 4 hours and promptly get the present invention after 12 hours.

The present invention can be used for removing poisonous and harmful substances such as sulfide in the natural gas, in the flue gas, oxysulfide, thioether, it can organic sulfide removal, can remove inorganic sulfur again, can remove the sulphur of ppm rank content, can remove again in every cubic metre of the sulfur content and reach 80 milligrams sulphur, desulfurization at normal temperatures again can desulfurization under 400-500 ℃ of temperature.Be used on the 300000 ton large-scale synthetic ammonia installations, organic sulfur in the natural gas and inorganic sulfur can be removed together, being used in the coal is the big power station of fuel, and it can remove the SO in the flue discharging gas ²

Renovation process of the present invention is: directly send into air with air blast toward the bed of desulphurization catalyst, the outlet that must open desulfurizer this moment, the valve of next production process is sent in cut-out, with the sulfur content of the gas that just can make air outlet slit in 20 minutes to 2 hours index, finish regenerative process less than technological requirement.

The specific embodiment

Below by embodiment the present invention is further described, but the present invention is not limited only to these examples.

Embodiment 1: with the catalyst weight is benchmark, adopts following prescription controlling catalyst:

ZnO..................64％

NiO..................1％

CaAlO ₃...............11％

TiO ₂.................0.5％

CoO..................0.9％

MoO..................0.7％

Al ₂O ₃................21.9％

Each component raw material in the above-mentioned prescription is mixed the back grinding in ball grinder 4～6 hours by the amount described in the prescription, be ground to the above fineness of 120 orders and must account for 30% of weight, after tablet machine is beaten sheet, crusher in crushing (being granulation) then, send into compression moulding in the ring squeezer after crossing 120 purposes sieve, again at 4kg/cm ²Still kettle in steam the roasting temperature of delivering to 400～500 ℃ of stove inherences after 4 hours and promptly get desulphurization catalyst after 12 hours.

The average pore size of this catalyst is 16.1nm, and pore volume is 1.5ml/g; Specific area is 400m ²/ g, bulk density is 1.08g/ml, compression strength is 150N/cm.

This catalyst is loaded in the devulcanizer, is used for removing the organic sulfur and the inorganic sulfur of natural gas, contain 80mg/m in this natural gas ³H ₂S, 1mg/m ³Mercaptan, 1mg/m ³Thioether, 20 ℃～600 ℃ temperature, the pressure of 3.5Mpa uses down this catalyst to carry out the desulfurization of natural gas, by the gas after the automatic sulphur analyzer test desulfurization, automatically crest does not appear in the sulphur analyzer, and the content that shows sulphur is significantly less than national standard below 0.1ppm.

This catalyst is after using the regular hour, must regenerate, the method of regeneration is: directly send into air with air blast toward the bed of desulphurization catalyst, the outlet that must open desulfurizer this moment, the valve of next production process is sent in cut-out, with the sulfur content of the gas that just can make air outlet slit in 20 minutes index, finish regenerative process less than technological requirement.Use after the cyclic regeneration 5 times, its sulfur limitation effect illustrates that with primary identical this activity of such catalysts still remains on the higher level.

Embodiment 2: with the catalyst weight is benchmark, adopts following prescription controlling catalyst:

ZnO..................9％

NiO..................0.5％

CaAlO ₃...............15％

TiO ₂.................0.5％

CoO..................2％

MoO..................3％

Al ₂O ₃................70％

The method of pressing among the embodiment 1 is produced catalyst, and the average pore size of this catalyst is 16.1nm, and pore volume is 0.5ml/g; Specific area is 450m ²/ g, bulk density is 1.08g/ml, compression strength is 170N/cm.

This catalyst is loaded in the devulcanizer, is used for removing with the coal SO of the discharging flue gas that is fuel ₂, contain 45mg/m in this discharging flue gas ³SO ₂, use this catalyst to discharge flue gas desulfurization at normal temperatures and pressures, the sulfur content in the gas after the desulfurization is below 1ppm.

The renovation process of this catalyst is identical with method among the embodiment 1, and only the time of regeneration needs 1 hour.

Claims (1)

1. a desulphurization catalyst is characterized in that with the catalyst weight being benchmark, contains the component of following percentage by weight:

ZnO..................6.5% to 65%

NiO..................0.5% to 2%

CaAlO ₃... ... 11% to 40%

TiO ₂... ... ... 0.5% to 2%

CoO..................0.9% to 2%

MoO..................0.7% to 3%

Al ₂O ₃... ... ... 20% to 70%

The average pore size of this catalyst is 16.1nm, and pore volume is 0.5～1.6ml/g; Specific area is 309～501m ²/ g, bulk density is 1.08g/ml, compression strength is 〉=150N/cm.