CN110127602A - The method of applications catalyst decomposing hydrogen sulfide - Google Patents
The method of applications catalyst decomposing hydrogen sulfide Download PDFInfo
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- CN110127602A CN110127602A CN201810136034.1A CN201810136034A CN110127602A CN 110127602 A CN110127602 A CN 110127602A CN 201810136034 A CN201810136034 A CN 201810136034A CN 110127602 A CN110127602 A CN 110127602A
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/02—Preparation of sulfur; Purification
- C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
- C01B17/0495—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by dissociation of hydrogen sulfide into the elements
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Abstract
The present invention relates to hydrogen sulfide to decompose field, disclose a kind of method of applications catalyst decomposing hydrogen sulfide, this method comprises: the unstripped gas containing hydrogen sulfide is introduced in reaction of low temperature plasma device, and it contacts under the conditions of dielectric barrier discharge with the decomposition catalyst in the reaction of low temperature plasma device to carry out decomposition reaction, it containing carrier, load active metal component on the carrier and auxiliary agent and the auxiliary agent is selected from least one of K, Na, N and P element in the decomposition catalyst；On the basis of the total weight of the decomposition catalyst, the content of the carrier is 40~90 weight %, and content of the active metal component in terms of oxide is 1~50 weight %, and content of the auxiliary agent in terms of oxide is 0.01~10 weight %.The method that the aforementioned method for improving hydrogen sulfide conversion ratio provided by the invention provides compared with the existing technology has higher hydrogen sulfide conversion ratio.
Description
Technical field
The present invention relates to hydrogen sulfide to decompose field, and in particular to a kind of method of applications catalyst decomposing hydrogen sulfide.
Background technique
Hydrogen sulfide (H2S it is) a kind of hypertoxic, stench sour gas, can not only causes the corrosion of the materials such as metal, but also
It is also easy to that catalyst poisoning is caused to inactivate in Chemical Manufacture；In addition, hydrogen sulfide can also be detrimental to health, cause environment dirty
Dye.Therefore, a large amount of hydrogen sulfide gas generated in the industrial circles such as petroleum, natural gas, coal and mineral products processing are carried out innoxious
When processing, no matter consider from process requirement, plant maintenance or environmental requirement etc., it is urgently to be resolved.
Crouse's (Claus) method processing hydrogen sulfide is industrially generallyd use at present, and method is by hydrogen sulfide partial oxidation
Obtain sulphur and water.Although the method solves the problems, such as the innoxious of hydrogen sulfide, but have lost a large amount of hydrogen resources.
With increasing for China's high sulfur bauxite amount, the sulfide hydrogen acid tail gas of hydrofinishing unit by-product is refined oil
Amount increases year by year, and amounts of hydrogen needed for hydrofinishing is consequently increased；In addition, hydrogen, as oil hydrogenation cracking, low-carbon alcohols are closed
At the primary raw material of, synthesis chemical engineering process such as ammonia, demand is also considerable.Therefore, hydrogen sulfide is directly decomposed is
One ideal hydrogen sulfide application technology as the second resource route, not only can make its innoxious, but also can produce hydrogen and elemental sulfur, no
Hydrogen resource recycling in petroleum refining process only may be implemented, it is a large amount of that conventional hydrocarbon-based reformation hydrogen production bring can also be reduced
CO2 emission.
Currently, hydrogen sulfide decomposition method specifically includes that high-temperature decomposition, electrochemical process, photocatalytic method and low-temperature plasma
Body method etc..In aforementioned a variety of methods, high temperature thermal decomposition method relative maturity in industrial technology, but hydrogen sulfide thermal decomposition is consumingly
Limited dependent on reaction temperature, and by thermodynamical equilibrium, though reaction temperature at 1000 DEG C or more, the conversion ratio of hydrogen sulfide
Only 20%.In addition, hot conditions are to the more demanding of reactor material, this also will increase operating cost.Further, since vulcanization
Hydrogen thermal decomposition conversion ratio is low, needs to separate a large amount of hydrogen sulfide gas from tail gas and recycle in systems, therefore also reduce
Unit efficiency and energy consumption is increased, these bring difficulty to its large industrialized application.Although using membrane technology can be with
Product is efficiently separated to break balance limitation, improves hydrogen sulfide conversion ratio, but thermal decomposition temperature tends to exceed the pole of film
Heat resisting temperature is limited, membrane material structure is destroyed.Electrochemistry rule there are operating procedures more, equipment seriously corroded, reaction are steady
The disadvantages of qualitative difference and low efficiency.Photocatalytic method decomposing hydrogen sulfide mainly uses for reference the research of photochemical catalyzing, research emphasis collection
In in terms of developing high efficiency semiconductor.Using solar energy come decomposing hydrogen sulfide, with low energy consumption, reaction condition temperature
It is relatively inexpensive method with simple operation and other advantages.But that there are treating capacities is small for this method, catalytic efficiency is low and is catalyzed
Agent is easy the problems such as inactivation.
Compared with other decomposition methods, low-temperature plasma body method has easy to operate, and device volume is small, and energy efficiency is high
The advantages that, and the reaction being directed to has the controllability of height, and it can be when small treating capacity, being difficult to focus on flexibly
It is applied on ground.Further, since it has the characteristics that high-energy density and can shorten the reaction time, can be realized at a lower temperature
Hydrogen sulfide is effectively decomposed, the changeable occasion of different scales, scattered distribution, working condition is suitable for.Moreover, recycling
While sulphur, hydrogen resource reclaim can be realized the utilization of hydrogen sulfide recycling by low-temperature plasma body method.
CN102408095A cooperates with decomposing hydrogen sulfide using dielectric barrier discharge and photochemical catalyst, and method is that will have light
The solid catalyst of catalytic activity is filled in plasma slab, however this method is decomposed the sulphur generated there are hydrogen sulfide and can be deposited
The shortcomings that below catalyst bed.
CN103495427A discloses the method for preparing load type metal sulfide catalyst using low temperature plasma, should
The prior art is characterized in, is uniformly distributed hydrogen sulfide gas or hydrogen sulfide containing gas ionization, formation by gas discharge
Low temperature plasma, utilize the low temperature plasma and load type metal salt precursor direct interaction to generate metal vulcanization
Object.Due to avoiding catalyst exposure at too high a temperature, the catalyst of preparation is not in hot agglomeration, thus
Particle size is smaller, and dispersion degree is higher.However, the prior art provide catalyst in the decomposition reaction for hydrogen sulfide,
The conversion ratio of hydrogen sulfide is not high.
Summary of the invention
It is decomposed the purpose of the invention is to the catalysed curing hydrogen for overcoming the prior art to provide and generates elemental sulfur and hydrogen
The not high defect of hydrogen sulfide conversion ratio existing for catalyst provides a kind of method of new applications catalyst decomposing hydrogen sulfide.
The present inventor has found under study for action, containing the auxiliary agent selected from least one of K, Na, N and P element at
When the decomposition catalyst of decomposing hydrogen sulfide of the catalyst divided in the reaction of low temperature plasma device for being used as dielectric barrier discharge,
The conversion ratio of hydrogen sulfide is enabled to significantly improve compared with the existing technology.Accordingly, the present inventor completes the present invention
Technical solution.
To achieve the goals above, the present invention provides a kind of method of applications catalyst decomposing hydrogen sulfide, this method comprises:
Unstripped gas containing hydrogen sulfide is introduced in reaction of low temperature plasma device, and low with this under the conditions of dielectric barrier discharge
Decomposition catalyst in isothermal plasma reactor is contacted to carry out decomposition reaction, wherein contains load in the decomposition catalyst
Body, the active metal component and auxiliary agent of load on the carrier, the carrier are in molecular sieve, aluminium oxide and silica
At least one, the active metal component are selected from group ib, group iib, group ivb, Group VB, group VIB, Section VII B
At least one of race, group VIII metallic element and the auxiliary agent are selected from least one of K, Na, N and P element；
On the basis of the total weight of the decomposition catalyst, the content of the carrier is 40~90 weight %, the active metal component
Content in terms of oxide is 1~50 weight %, and content of the auxiliary agent in terms of oxide is 0.01~10 weight %.
The method that the aforementioned method for improving hydrogen sulfide conversion ratio provided by the invention provides compared with the existing technology has more
High hydrogen sulfide conversion ratio；Particularly, in the preferred case, method provided by the invention enables to the conversion ratio of hydrogen sulfide to exist
Stable higher level is maintained in the relatively long time.
In addition, preceding method provided by the invention have the advantages that it is easy to operate and at low cost.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of reaction of low temperature plasma device used in the embodiment of the present invention.
Description of symbols
1, inner cylinder 2, outer cylinder
11, reactor inlet 21, heat-conducting medium entrance
12, product gas outlet 22, heat-conducting medium outlet
13, liquid product outlet
3, central electrode
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
As previously mentioned, the present invention provides a kind of methods of applications catalyst decomposing hydrogen sulfide, this method comprises: will contain
The unstripped gas of hydrogen sulfide is introduced in reaction of low temperature plasma device, and under the conditions of dielectric barrier discharge with the low temperature etc. from
Decomposition catalyst in daughter reactor is contacted to carry out decomposition reaction, wherein contains carrier, load in the decomposition catalyst
Active metal component and auxiliary agent on the carrier, the carrier are at least one in molecular sieve, aluminium oxide and silica
Kind, the active metal component is selected from group ib, group iib, group ivb, Group VB, group VIB, V Group IIB, the
At least one of group VIII metal element and the auxiliary agent are selected from least one of K, Na, N and P element；With described
On the basis of the total weight of decomposition catalyst, the content of the carrier is 40~90 weight %, and the active metal component is to aoxidize
The content of object meter is 1~50 weight %, and content of the auxiliary agent in terms of oxide is 0.01~10 weight %.
It is preferably described on the basis of the total weight of the decomposition catalyst in order to further increase the conversion ratio of hydrogen sulfide
The content of carrier is 62~85 weight %, and content of the active metal component in terms of oxide is 7~30 weight %, described to help
Content of the agent in terms of oxide is 0.1~8 weight %.
In particularly preferred situation, in the decomposition catalyst, the auxiliary agent is K and/or Na.The present inventor's hair
It is existing, when selecting K and/or Na as auxiliary agent in the decomposition catalyst of method of the invention, method of the invention is enabled to obtain
Obtain considerably higher hydrogen sulfide conversion ratio.
According to a kind of preferred embodiment, in the decomposition catalyst, containing as component A in the carrier
Molecular sieve and aluminium oxide and/or silica as component B.
Under preferable case, in the decomposition catalyst, the content weight ratio of the preferably described component A and the component B are
1:(0.01~1.2)；Preferably 1:(0.02~1)；More preferably 1:(0.05~0.95)；Further preferably 1:(0.1~
0.8)。
In the method for the invention, under the conditions of dielectric barrier discharge, when the institute contained in reaction of low temperature plasma device
It states and contains auxiliary agent in decomposition catalyst, and contain molecular sieve and the conduct as component A in the carrier in the decomposition catalyst
The content weight ratio of the aluminium oxide and/or silica of component B and the component A and the component B are of the invention above-mentioned excellent
When selecting in range, method of the invention can obtain higher hydrogen sulfide conversion ratio under relatively lower energy consumption.
Under preferable case, in the decomposition catalyst, the molecular sieve is in mesoporous molecular sieve and large pore molecular sieve
At least one.
Preferably, the average pore size of the mesoporous molecular sieve is more than or equal to 0.3nm to less than 0.6nm；The macropore point
The average pore size of son sieve is 0.6~1.0nm.
Preferably, the medium-pore molecular screened from ZSM-35, ZSM-48, ZSM-5, ZSM-11, ZSM-22, ZSM-23,
At least one of ZSM-12, ZSM-57 and SAPO-11.
Preferably, the Large pore molecular is screened from ZSM-20, SAPO-5, USY, ZSM-3, SAPO-37, beta-molecular sieve, MCM-
At least one of 68 and modenite.
According to a kind of preferred embodiment, in the decomposition catalyst, the molecular sieve is mesoporous molecular sieve
With the mixture of large pore molecular sieve.
Preferably, in the decomposition catalyst, the content weight ratio of the mesoporous molecular sieve and the large pore molecular sieve
For 1:(0.05~0.85)；More preferably 1:(0.1~0.8)；Further preferably 1:(0.25~0.55).
It was found by the inventors of the present invention that when containing mesoporous molecular sieve and large pore molecular sieve in the decomposition catalyst simultaneously,
And the weight ratio of the two is when stating in preferred scope before this invention, using the decomposition catalyst in reaction of low temperature plasma device
When the decomposition reaction of catalysed curing hydrogen, the conversion ratio of hydrogen sulfide can be significantly improved, and the conversion ratio of hydrogen sulfide is stablized
Maintain higher level.
Under preferable case, in the decomposition catalyst, the active metal component be selected from Cu, Ag, Zn, Cd, Ti,
At least one of Zr, V, Cr, Mo, W, Mn, Fe, Co, Ni, Pd and Pt metallic element；It is highly preferred that the active metal component
For selected from least one of Ti, Zr, Mo, W, Mn, Co, Ni and Cr metallic element.
According to a kind of preferred embodiment, in the decomposition catalyst, the active metal component be containing
The mixture of first metallic element and the second metallic element, first metallic element are Ti and/or Zr, the second metal member
Element is Co and/or Ni.
Preferably, the content weight ratio of first metallic element and second metallic element is 1:(0.5~2).
In the decomposition catalyst of the invention, the active metal component can with metal oxide, metal salt or
The form of person's metal sulfide exists, and the preferably described active metal component is deposited in the form of metal oxide or metal sulfide
?.
There is no particular limitation to the method for preparing the decomposition catalyst for method of the invention, can be normal using this field
Prepared by the method for preparing catalyst of rule, as long as the decomposition catalyst with preceding feature of the present invention can be obtained.
Under preferable case, aforementioned decomposition catalyst of the invention is microspheric, and the average grain diameter of the decomposition catalyst
For 0.1~50mm.
Preferably, it is 5~30kV that the discharging condition, which includes: discharge voltage, and discharge frequency is 200~30000Hz, electric discharge
Electric current is 0.1~100A.
Under preferable case, the condition of the decomposition reaction includes: that reaction temperature is 0~800 DEG C, preferable reaction temperature 0
~200 DEG C, reaction pressure is -0.06MPa to 0.6MPa, residence time of the reactant in the reaction of low temperature plasma device
It is 1 × 10-5~120s.
There is no particular limitation for structure of the method provided by the invention to reaction of low temperature plasma device, and of the invention is specific
Instance section provides only a kind of reaction of low temperature plasma device of specific structure, ability in order to illustrate the effect of the method for offer
Field technique personnel should not be construed as limiting the invention.
The present invention will be described in detail by way of examples below.In following embodiment, in the feelings being not particularly illustrated
Under condition, the various raw materials used are all from commercially available.
Decomposition catalyst used in following instance is all made of to be prepared following preparation method: by carrier with optionally contain
Binder mixing, the then extrusion molding on banded extruder, then the dry 2h at 120 DEG C, then roasts 6h at 300 DEG C,
Obtain catalyst carrier.
Take the metal salt solution of 100g carrier and the element containing active metal component and the salting liquid containing auxiliary element
Mixing is to carry out impregnation, and then the dry 2h at 120 DEG C, then roasts 5h at 320 DEG C, obtain corresponding catalyst.
The composition for the catalyst being prepared using the above method is as follows:
Cat1: with the total weight of decomposition catalyst, active metal component (Ti and Co, and Ti and Co element wt ratio is
1:1) content in terms of oxide is 16.8 weight %, and the content of gama-alumina is 26.9 weight %, K2The content of O is 3.2 weights
% is measured, the content of ZSM-23 molecular screen is 34.6 weight %, and surplus is beta-molecular sieve.
Cat2: with the total weight of decomposition catalyst, active metal component (Zr and Ni, and Zr and Ni element wt ratio is
1:0.65) content in terms of oxide is 25.9 weight %, and the content of silica is 27.6 weight %, K2The content of O is 5.6 weights
% is measured, the content of ZSM-35 molecular sieve is 27.6 weight %, and surplus is ZSM-3 molecular sieve.
Cat3: with the total weight of decomposition catalyst, active metal component (Ti and Ni, and Ti and Ni element wt ratio is
1:1.65) content in terms of oxide is 13.2 weight %, and the content of gama-alumina is 14.5 weight %, Na2The content of O is
The content of 1.8 weight %, ZSM-11 molecular sieves is 52.6 weight %, and surplus is SAPO-37 molecular sieve.
Cat4: with the total weight of decomposition catalyst, active metal component (Ti and Co, and Ti and Co element wt ratio is
1:1) content in terms of oxide is 16.6 weight %, and the content of gama-alumina is 24.6 weight %, K2The content of O is 9.3 weights
% is measured, the content of ZSM-23 molecular screen is 30.2 weight %, and surplus is beta-molecular sieve.
Cat5: with the total weight of decomposition catalyst, active metal component (Zr and Ni, and Zr and Ni element wt ratio is
1:0.65) content in terms of oxide is 26.2 weight %, and the content of silica is 26.9 weight %, P2O5Content be 5.8 weights
% is measured, the content of ZSM-35 molecular sieve is 28.3 weight %, and surplus is ZSM-3 molecular sieve.
Cat6: with the total weight of decomposition catalyst, active metal component (Ti and Ni, and Ti and Ni element wt ratio is
1:1.65) content in terms of oxide is 13.2 weight %, Na2The content of O is the content of 1.9 weight %, ZSM-11 molecular sieves
For 67.1 weight %, surplus is SAPO-37 molecular sieve.
Cat7: with the total weight of decomposition catalyst, active metal component (Ti and Co, and Ti and Co element wt ratio is
1:1) content in terms of oxide is 16.5 weight %, and the content of gama-alumina is 27.3 weight %, K2The content of O is 3.4 weights
% is measured, surplus is ZSM-23 molecular screen.
D-Cat1: with the total weight of decomposition catalyst, active metal component (Ti and Co, and Ti and Co element wt ratio
It is 16.7 weight % for content of the 1:1) in terms of oxide, surplus is gama-alumina.
D-Cat2: with the total weight of decomposition catalyst, active metal component (Ti and Co, and Ti and Co element wt ratio
It is 16.9 weight % for content of the 1:1) in terms of oxide, the content of ZSM-23 molecular screen is 53.6 weight %, and surplus is beta molecule
Sieve.
D-Cat3: with the total weight of decomposition catalyst, active metal component (Zr and Ni, and Zr and Ni element wt ratio
It is 26.3 weight % for content of the 1:0.65) in terms of oxide, the content of silica is 28.0 weight %, ZSM-35 molecular sieve
Content is 14.2 weight %, and surplus is ZSM-3 molecular sieve.
Embodiment 1
Embodiment carries out the decomposition reaction of hydrogen sulfide, specifically, Fig. 1 using reaction of low temperature plasma device shown in FIG. 1
Shown in reaction of low temperature plasma device structure are as follows:
Reactor includes:
Inner cylinder 1 is respectively arranged with reactor inlet 11, product gas outlet 12 and liquid product outlet on the inner cylinder
13, wherein whole side walls of the inner cylinder are formed by block media, and the material for forming the block media is hard glass,
Every time in test, the catalyst of total 200mL is loaded in reactor inner cylinder, the filling type of catalyst is as shown in table 1；
Outer cylinder 2, the outer cylinder is nested in the outside of the inner cylinder, and heat-conducting medium entrance is respectively arranged on the outer cylinder
21 and heat-conducting medium outlet 22；
The axial centerline of the inner cylinder is arranged in central electrode 3, the central electrode, forms the central electrode
Material is stainless steel metal stick；
Full of heat-conducting medium, (NaCl of specially 15 weight % is water-soluble in space between the inner wall of outer cylinder and the outer wall of inner cylinder
Liquid), which also functions simultaneously as liquid grounding electrode；
The distance between the inner sidewall of the lateral wall of the central electrode and block media L1With the thickness of block media
Spend D1Ratio be 6:1；
Height H of the setting position of product gas outlet relative to inner cylinder bottom1With the electric discharge containing block media
The length L in region2Between proportionate relationship are as follows: H1: L2=1:30；
The volume of the reactor inner cylinder of the present embodiment is 500mL.
Gas containing hydrogen sulfide enters in reactor inner cylinder from the top of reactor inner cylinder, and from positioned at reactor inner cylinder
The product gas outlet of lower part draws gaseous product, and elemental sulfur is drawn from the liquid product outlet for being located at reactor bottom；And
Heat-conducting medium is introduced from the lower part of the outer cylinder of reactor, and is drawn from the top of the outer cylinder of reactor.
The operating procedure of reaction of low temperature plasma device:
It is passed through nitrogen into the inner cylinder of reaction of low temperature plasma device from reactor inlet, to remove the sky in region of discharge
Gas, and gas is drawn from product gas outlet and liquid product outlet.Meanwhile it introducing and leading into outer cylinder from heat-conducting medium entrance
Thermal medium, the heat-conducting medium of introducing is exported from heat-conducting medium draws, and the temperature of heat-conducting medium remains 40 DEG C.
Then H is passed through into the inner cylinder of reaction of low temperature plasma device from reactor inlet2S/Ar gaseous mixture, wherein H2S body
Fraction is 30%, and control gaseous mixture flow velocity makes gas in the mean residence time of region of discharge be 17.6s, and reaction pressure is
0.02MPa。H2After S/Ar gaseous mixture is passed through reactor 30min, ac high voltage source is connected, by adjusting during voltage and frequency make
Plasma discharge field is formed between heart electrode and liquid grounding electrode.
Wherein discharging condition are as follows: voltage 17.2kV, frequency 7.8kHz, electric current 0.75A.Hydrogen sulfide gas is discharging
Region ionizes, and is decomposed into hydrogen and elemental sulfur, and the elemental sulfur for generation of discharging slowly is flowed down along inner tube wall, and from product liquid
Outlet outflow.Gas is flowed out from product gas outlet after reaction.
It persistently carries out testing H respectively under 10min, 20min and 60min in decomposition reaction2As a result S conversion ratio is listed in table 1
In.
Table 1
Embodiment 2
The present embodiment is carried out using method similar to Example 1, and unused institute is discharging condition in the present embodiment are as follows:
Voltage is 18.5kV, frequency 8.0kHz, electric current 0.75A.
And the condition of decomposition reaction are as follows: reaction temperature is 60 DEG C, and reaction pressure 0.05MPa, reactant is in the low temperature
Mean residence time in plasma reactor is 18.2s.
Remaining is in the same manner as in Example 1.
The results are shown in Table 2 for the present embodiment.
Table 2
Can be seen that method provided by the invention from the result of Tables 1 and 2 significantly improves the conversion ratio of hydrogen sulfide；
Also, it is higher that method provided by the invention enables to the conversion ratio of the hydrogen sulfide in the decomposition reaction of hydrogen sulfide to be stably maintained at
It is horizontal.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (13)
1. a kind of method of applications catalyst decomposing hydrogen sulfide, this method comprises: the unstripped gas containing hydrogen sulfide is introduced to low
In isothermal plasma reactor, and it is catalyzed under the conditions of dielectric barrier discharge with the decomposition in the reaction of low temperature plasma device
Agent is contacted to carry out decomposition reaction, wherein contains carrier, the active metal of load on the carrier in the decomposition catalyst
Component and auxiliary agent, the carrier are at least one of molecular sieve, aluminium oxide and silica, and the active metal component is choosing
At least one from group ib, group iib, group ivb, Group VB, group VIB, V Group IIB, group VIII metallic element
Kind and the auxiliary agent are selected from least one of K, Na, N and P element；Using the total weight of the decomposition catalyst as base
Standard, the content of the carrier are 40~90 weight %, and content of the active metal component in terms of oxide is 1~50 weight
% is measured, content of the auxiliary agent in terms of oxide is 0.01~10 weight %.
2. according to the method described in claim 1, wherein, on the basis of the total weight of the decomposition catalyst, the carrier
Content is 62~85 weight %, and content of the active metal component in terms of oxide is 7~30 weight %, and the auxiliary agent is with oxygen
The content of compound meter is 0.1~8 weight %.
3. according to the method described in claim 1, wherein, the auxiliary agent is K and/or Na.
4. method described in any one of -3 according to claim 1, wherein in the decomposition catalyst, in the carrier
Containing the molecular sieve as component A and as the aluminium oxide and/or silica of component B.
5. according to the method described in claim 4, wherein, the content weight ratio of the component A and the component B are 1:(0.01
~1.2)；Preferably 1:(0.05~0.95)；More preferably 1:(0.1~0.8).
6. according to the method described in claim 4, wherein, in the decomposition catalyst, the molecular sieve is selected from medium-pore molecular
At least one of sieve and large pore molecular sieve；Preferably,
The average pore size of the mesoporous molecular sieve is more than or equal to 0.3nm to less than 0.6nm；The average hole of the large pore molecular sieve
Diameter is 0.6~1.0nm.
7. according to the method described in claim 4, wherein, the medium-pore molecular is screened from ZSM-35, ZSM-48, ZSM-5, ZSM-
11, at least one of ZSM-22, ZSM-23, ZSM-12, ZSM-57 and SAPO-11；
The Large pore molecular is boiled screened from ZSM-20, SAPO-5, USY, ZSM-3, SAPO-37, beta-molecular sieve, MCM-68 and mercerising
At least one of stone.
8. the method according to any one of claim 4-7, wherein in the decomposition catalyst, the molecular sieve
For the mixture of mesoporous molecular sieve and large pore molecular sieve.
9. according to the method described in claim 8, wherein, in the decomposition catalyst, the mesoporous molecular sieve and described big
The content weight ratio of porous molecular sieve is 1:(0.05~0.85)；Preferably 1:(0.25~0.55).
10. method described in any one of -3 according to claim 1, wherein in the decomposition catalyst, the activity gold
Category group is divided into selected from least one of Cu, Ag, Zn, Cd, Ti, Zr, V, Cr, Mo, W, Mn, Fe, Co, Ni, Pd and Pt metal member
Element；Preferably,
The active metal component is selected from least one of Ti, Zr, Mo, W, Mn, Co, Ni and Cr metallic element.
11. according to the method described in claim 10, wherein, in the decomposition catalyst, the active metal component be containing
There is the mixture of the first metallic element and the second metallic element, first metallic element is Ti and/or Zr, second metal
Element is Co and/or Ni；Preferably,
The content weight ratio of first metallic element and second metallic element is 1:(0.5~2).
12. method described in any one of -3 according to claim 1, wherein the discharging condition includes: that discharge voltage is 5
~30kV, discharge frequency are 200~30000Hz, and discharge current is 0.1~100A.
13. method described in any one of -3 according to claim 1, wherein the condition of the decomposition reaction includes: reaction temperature
Degree is 0~800 DEG C, and reaction pressure is -0.06MPa to 0.6MPa, and reactant stops in the reaction of low temperature plasma device
Staying the time is 1 × 10-5~120s.
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| RU2777440C2 (en) * | 2021-01-11 | 2022-08-03 | Анатолий Николаевич Старцев | Catalyst for producing hydrogen and diatomic gaseous sulphur in the process of decomposition of hydrogen sulphide |
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