CN106423287A - Supported mercury-free catalyst, preparation method thereof and application of supported mercury-free catalyst in preparation of vinyl chloride through ethyne hydrochlorination - Google Patents
Supported mercury-free catalyst, preparation method thereof and application of supported mercury-free catalyst in preparation of vinyl chloride through ethyne hydrochlorination Download PDFInfo
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
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Abstract
The invention relates to the technical field of catalysts, and provides a supported mercury-free catalyst, a preparation method thereof and an application of the supported mercury-free catalyst in preparation of vinyl chloride through ethyne hydrochlorination. The supported mercury-free catalyst is prepared through steps as follows: step one, preparing a precursor solution of active components; step two, supporting the active components on a metal-organic framework porous material with an isovolumetric or an over-volumetric impregnation method to obtain the green and environment-friendly supported mercury-free catalyst. The supported mercury-free catalyst is good in stability, and under the same technological condition, activity and selectivity of the supported mercury-free catalyst are higher or equal to those of a conventional industrial mercury catalyst; meanwhile, the application of the supported mercury-free catalyst prepared from the metal-organic framework porous material as a supporter in preparation of vinyl chloride through ethyne hydrochlorination is proposed for the first time, and vinyl chloride monomers can be prepared in a diversified and environment-friendly manner, so that the environmental pollution and the potential safety hazard caused by the industrial mercury catalyst are greatly reduced.
Description
Technical field
The present invention relates to catalyst technical field, it is a kind of support type catalyst without mercury and preparation method thereof and in acetylene hydrogen
The application in vinyl chloride is prepared in chlorination.
Background technology
, as one of big general engineering plastic in the world five, the synthetic technology of VCM (VCM) is non-for polyvinyl chloride (PVC)
The normally off key, synthesizing VCM at present mainly has acetylene method, ethane method, three kinds of processes of ethylene process.Based on the current petroleum resources of China
Shortage, the energy resource structure of coal resources relative abundance, produce VCM and mainly adopt acetylene method, and afterwards in longer period of time
It is still the main production that China produces VCM.Adopt acetylene method to produce the acetylene hydrochlorination reaction of VCM at present, be with activity
Charcoal load HgCl2 is catalyst, carries out in fixed bed reactors.Because, in actual production process, mercury catalyst is in high temperature
Under the conditions of because distillation cause run off, also social environment can be polluted, the safety of people is worked the mischief.In addition, China's mercury money
Source shortage, depends on import.These are all that existing acetylene method produces the main bugbear that VCM faces, and realize acetylene hydrochlorination
The mercuryless key being to solve these problems of catalyst.
Metallic organic framework porous material (Metal Organic Frameworks, MOFs) be a class by organic ligand and
The novel porous materials having recurrent network structure that inorganic metal center or metal cluster are formed by coordination, its high hole
Rate, bigger serface, and can the aperture of modulation and Space expanding be that traditional inorganic porous material can not be compared.
Just because of these advantages are so that the application Showed Very Brisk in many fields for the MOFs material, achievement in research emerges in an endless stream, also so that
MOFs material is of increased attention.At present, MOFs material stores in gas, gas separating-purifying, insoluble drug release, raw
The application of thing enzyme and catalytic reaction aspect is attracted attention the most, is also the Main way that science team of various countries endeavours to study.
At present, metallic organic framework porous material is widely used to catalytic field, and metallic organic framework porous material
May also pass through regulation and control modification and obtain more preferable catalytic effect.Such as MOF-5, UIO-66, IRMOFs-3, Mg-MOFs-74,
The metallic organic framework porous material such as HKUST-1, ZIF-8, MOF-53, is applied to synthesize the anti-of ring lake carbonic ester as catalyst
Answer in system.Selenole is referred on MOFs as sensitising agent by patent CN 105481888A, and prepared catalyst is applied to
In light-catalyzed reaction, there is preferable effect.Patent CN 104785298A adopts Bearing score Xi Er skeletal porous material
(Material of Institute Lavoisier Frameworks, abbreviation MILs), as carrier, the support type of preparation is solid
Body base catalyst, has critically important using value in ester exchange Synthesis of dimethyl carbonate.Au3+ active component is disperseed by Zhang
Form Au3+ loaded catalyst on metallic organic framework porous material IRMOF-3, apply and be coupled in aldehyde, alkynes and amine three component
In reaction, there is preferable catalysis activity [Zhang X, Xamena F X L I, Corma A.gold (III)-metal
organic framework bridges the gap between homogeneous and heterogeneous gold
catalysts[J].Journal of Catalysis,2009,265(2):155-160].The Wang Yu problem of Beijing University of Technology
Group using metallic organic framework porous material Cu-MOF loaded Cu (NO3) 2 2-in-1 with Cu (CH3COO) become catalyst, CO's
Have in gas phase reaction good catalytic effect [Wang Yu. metal-organic framework materials (Cu-BTC) catalysis CO oxidation [D]. Beijing
Polytechnical university, 2012].
In acetylene hydrochlorination reaction, laboratory is with Carbon Materials (especially absorbent charcoal material) as carrier mostly, and bears
Carry active component as research object, such as patent CN 102282112A loads Au nanometer on the Carbon Materials of high-ratio surface
Grain, is made for the catalyst of 1wt%Au content, and this catalyst has identical catalysis characteristics with traditional mercury catalyst；Patent CN
101249451A, with activated carbon as carrier, is prepared for Au and the multicomponent catalyst of other base metals mixing, Au in catalyst
Load capacity is 0.5wt%, and when acetylene air speed is 250h-1, the conversion ratio of acetylene can reach 95% to 98%.Patent CN
In 101947465A, Luo etc. be prepared for add noble metal (Pt, Ru, Rh and Pd) and some base metals (Cu, Zn, K, Ba with
Ni Au base catalyst).In catalyst, the load capacity of Au is 0.05wt% to 0.5wt%, when acetylene air speed is 400h-1, second
Alkyne conversion rate can reach 85%, and catalyst can regenerate use.Zhang etc. in patent CN 102336631A, by Co
It is added in Au base catalyst with La, compare the impact to catalysis activity for the different carriers, the active charcoal of carrier of research, silicon
Glue, charcoal silicon and molecular sieve, other auxiliary agents also include K, Na, Bi, Fe, Cu, Zn, and the wherein load capacity of Au is 1%, when acetylene air speed
During for 360h-1, the conversion ratio of acetylene can reach 98.4%.Zhang etc. adopts thiocarbamide, rhodanate as part, K, Co, Cu
With Zn as collaborative metal, the load capacity of Au is 1wt%, and when acetylene air speed is 360h-1, the conversion ratio of acetylene can reach
92% [CN 103191760A].Luo etc., in patent CN 103381369A, is adulterated carbon nanotube using N-, Graphene or Jie
As carrier, the load capacity of Au is 0.35wt% to hole charcoal, and when acetylene air speed is 600h-1, the conversion ratio of acetylene is permissible 80%
Maintain for a long time.In addition, the carrier of catalyst needed for acetylene hydrochlorination is not limited merely to Carbon Materials, such as in patent CN
In 102302946A, Li Wei etc. adopts MCM-41 as carrier-supported precious metal catalyst, also has preferably in acetylene hydrochlorination
Activity.13X is adopted, the different kinds of molecules such as MCM-41 sieves as carrier, and active component mercury chloride is born in patent CN 101890360A
It is loaded on carrier, and add metallic compound in preparation process as auxiliary agent, prepared new catalyst, anti-in acetylene hydrochlorination
Ying Zhongyou preferably selectivity and higher yield.
At present, relevant metallic organic framework porous material is not also had to react in acetylene hydrochlorination as support applications
Relevant report.
Content of the invention
The invention provides a kind of support type catalyst without mercury and preparation method thereof and in preparing chloroethylene by acetylene hydrochlorination
In application, overcome the deficiency of above-mentioned prior art, its can effectively solving also there is no relevant metallic organic framework porous material
The problem of the relevant report reacted in acetylene hydrochlorination as support applications.
One of technical scheme is realized by following measures：A kind of support type catalyst without mercury, presses
The method of stating obtains：The first step, by the sulfate of the nitrate of the chloride of active component or active component or active component or work
Property component the dissolving of phosphate solvent after obtain the precursor solution of active component；Second step, by equi-volume impregnating or mistake
Volume impregnation method metallic organic framework porous material is added in the precursor solution of active component and is impregnated, warp after dipping
After dry, nitrogen protects lower roasting and compressing tablet, obtain support type catalyst without mercury.
Further optimization and/or improvements to foregoing invention technical scheme one of are presented herein below：
Above-mentioned active component be Bi or Cu or Sn or Co or Au or Pd or Pt or Ru or Ir or therein more than one；Or/
With in support type catalyst without mercury, the percent mass load capacity of active component is 0.5% to 30%.
Above-mentioned solvent is deionized water or acetonitrile；Or/and, the presoma of metallic organic framework porous material and active component
Solution is 1 by volume:1 to 1:3 mixing.
Above-mentioned baking temperature is 90 DEG C to 110 DEG C, and drying time is 10h to 24h；Or/and, sintering temperature is for 120 DEG C extremely
350 DEG C, roasting time is 2h to 8h；Or/and, N2 pressure is 0.01MPa to 0.2MPa.
The two of technical scheme are realized by following measures：A kind of preparation of support type catalyst without mercury
Method, is carried out in the steps below：The first step, by the sulphur of the nitrate of the chloride of active component or active component or active component
The precursor solution of active component is obtained after the phosphate solvent dissolving of hydrochlorate or active component；Second step, by equal-volume leaching
Stain method or excessively volume impregnation method metallic organic framework porous material are added in the precursor solution of active component and are impregnated,
After dipping after drying, the lower roasting of nitrogen protection and compressing tablet, obtain support type catalyst without mercury.
To foregoing invention technical scheme two further optimization and/or improvements are presented herein below：
Above-mentioned active component be Bi or Cu or Sn or Co or Au or Pd or Pt or Ru or Ir or therein more than one；Or/
With in support type catalyst without mercury, the percent mass load capacity of active component is 0.5% to 30%.
Above-mentioned solvent is deionized water or acetonitrile；Or/and, the presoma of metallic organic framework porous material and active component
Solution is 1 by volume:1 to 1:3 mixing.
Above-mentioned baking temperature is 90 DEG C to 110 DEG C, and drying time is 10h to 24h；Or/and, sintering temperature is for 120 DEG C extremely
350 DEG C, roasting time is 2h to 8h；Or/and, N2 pressure is 0.01MPa to 0.2MPa.
The three of technical scheme are realized by following measures：A kind of support type catalyst without mercury is in acetylene
Hydrogen chloride prepares the application in vinyl chloride.
Active component is supported on metallic organic framework porous by equi-volume impregnating or volume impregnation method excessively by the present invention
On material, obtain the support type catalyst without mercury of environmental protection, support type catalyst without mercury good stability of the present invention, in identical
Under process conditions, the activity and selectivity of support type catalyst without mercury of the present invention is higher than or suitable with existing industry mercury catalyst；
Meanwhile, present invention firstly provides metallic organic framework porous material is carrier, the support type catalyst without mercury of preparation is in acetylene
Hydrogen chloride prepares the application in vinyl chloride, can variation, produce VCM to environmental protection, greatly reduce industrial mercury
Catalyst is to the pollution of environment and potential safety hazard.
Specific embodiment
The present invention is not limited by following embodiments, can technology according to the present invention scheme determine specifically with actual conditions
Embodiment.
Embodiment 1, this support type catalyst without mercury is obtained by following preparation methods：The first step, by the chlorination of active component
Activity is obtained after the phosphate solvent dissolving of the sulfate of the nitrate of thing or active component or active component or active component
The precursor solution of component；Metallic organic framework porous material is added by second step by equi-volume impregnating or volume impregnation method excessively
Enter and impregnated in the precursor solution of active component, after dipping after drying, the lower roasting of nitrogen protection and compressing tablet, born
Load type catalyst without mercury.Metallic organic framework porous material is existing public, and metallic organic framework porous material has MOF-
5th, HKUST-1, UIO series, ZIF series, MIL series, IRMOF series and MOF-53 etc.；Metallic organic framework porous material can
Using solvent evaporation method, hydro-thermal method, solvent-thermal method, supercritical ultrasonics technology, microwave assisting method, electrochemical process, ion thermal synthesis method and list
Prepared by the methods such as brilliant conversion method.
Embodiment 2, as the optimization of above-described embodiment, active component is Bi or Cu or Sn or Co or Au or Pd or Pt or Ru
Or Ir or therein more than one；Or/and, in support type catalyst without mercury, the percent mass load capacity of active component is 0.5%
To 30%.
Embodiment 3, as the optimization of above-described embodiment, solvent is deionized water or acetonitrile；Or/and, metallic organic framework
The precursor solution of porous material and active component is 1 by volume:1 to 1:3 mixing.
Embodiment 4, as the optimization of above-described embodiment, baking temperature is 90 DEG C to 110 DEG C, and drying time is for 10h extremely
24h；Or/and, sintering temperature is 120 DEG C to 350 DEG C, and roasting time is 2h to 8h；Or/and, N2 pressure is for 0.01MPa extremely
0.2MPa.
Embodiment 5, this support type catalyst without mercury is obtained by following preparation methods：The first step, weighs 0.36g BiCl3 molten
Enter in the deionized water of 10mL, dropwise dropping hydrochloric acid is completely dissolved to BiCl3, obtains the precursor solution of Bi after dissolving；Second
Step, weighs 1.60g metallic organic framework porous material Cu-MOFs, and metallic organic framework porous material Cu-MOFs is added Bi's
In precursor solution, stirring dipping 24h, 10h is dried at temperature is 100 DEG C after dipping, under nitrogen protection in temperature after being dried
Spend for roasting 4h at 120 DEG C, N2 pressure is 0.01MPa, through compressing tablet after roasting, obtains support type catalyst without mercury.Embodiment 5
To support type catalyst without mercury in Bi percent mass load capacity be 15%.
In embodiment 5, metallic organic framework porous material Cu-MOFs can be commercially available, also can obtain as follows：With molten
The method synthesis metallic organic framework porous material Cu-MOFs of agent heat, first, weighs 5.00gCu (NO3) 2, adds 25mL to it
Deionized water, stirring so that it is dissolved；Separately weigh trimesic acid 1.00g, add DMF and C2H5OH (DMF to it:C2H5OH
=1:3, v/v) then above two solution mixed, magnetic agitation 30min, more ultrasonic 30min by mixed solution 50mL, will
Solution is transferred to in teflon-lined autoclave, putting in 120 DEG C of drying box, crystallization 10h, reaction
After end, naturally cool to room temperature, centrifugation, washing, be vacuum dried 10h, obtain navy blue metallic organic framework porous material
Material Cu-MOFs.
Embodiment 6, this support type catalyst without mercury is obtained by following preparation methods：The first step, weighs 0.48g BiCl3 molten
Enter in the deionized water of 10mL, dropwise dropping hydrochloric acid is completely dissolved to BiCl3, obtains the precursor solution of Bi after dissolving；Second
Step, weighs 1.60g metallic organic framework porous material Cu-MOFs, and metallic organic framework porous material Cu-MOFs is added Bi's
In precursor solution, stirring dipping 24h, 10h is dried at temperature is 100 DEG C after dipping, under nitrogen protection in temperature after being dried
Spend for roasting 8h at 120 DEG C, N2 pressure is 0.01MPa, through compressing tablet after roasting, obtains support type catalyst without mercury.Embodiment 6
To support type catalyst without mercury in Bi percent mass load capacity be 20%.
In embodiment 6, metallic organic framework porous material Cu-MOFs can be commercially available, also can be organic by metal in embodiment 5
The preparation method of skeletal porous material C u-MOFs obtains.
Embodiment 7, this support type catalyst without mercury is obtained by following preparation methods：The first step, weighs 0.60g BiCl3 molten
Enter in the deionized water of 10mL, dropwise dropping hydrochloric acid is completely dissolved to BiCl3, obtains the precursor solution of Bi after dissolving；Second
Step, weighs 1.60g metallic organic framework porous material Cu-MOFs, and metallic organic framework porous material Cu-MOFs is added Bi's
In precursor solution, stirring dipping 24h, 10h is dried at temperature is 100 DEG C after dipping, under nitrogen protection in temperature after being dried
Spend for roasting 4h at 120 DEG C, N2 pressure is 0.01MPa, through compressing tablet after roasting, obtains support type catalyst without mercury.Embodiment 7
To support type catalyst without mercury in Bi percent mass load capacity be 25%.
In embodiment 7, metallic organic framework porous material Cu-MOFs can be commercially available, also can be organic by metal in embodiment 5
The preparation method of skeletal porous material C u-MOFs obtains.
Embodiment 8, this support type catalyst without mercury is obtained by following preparation methods：The first step, weighs 0.63g Bi (NO3)
In 3 deionized waters dissolving in 10mL, dropwise dropping HNO3 to Bi (NO3) 3 is completely dissolved, and the presoma obtaining Bi after dissolving is molten
Liquid；Second step, weighs 1.80g metallic organic framework porous material MIL-53 (Al), by metallic organic framework porous material MIL-
53 (Al) adds in the precursor solution of Bi, stirring dipping 24h, 10h is dried after dipping at temperature is 100 DEG C, after being dried
Nitrogen protection under temperature be 350 DEG C at roasting 6h, N2 pressure be 0.01MPa, through compressing tablet after roasting, obtain support type mercury-free and urge
Agent.In the support type catalyst without mercury that embodiment 8 obtains, the percent mass load capacity of Bi is 15%.
In embodiment 8, metallic organic framework porous material MIL-53 (Al) can be commercially available, also can obtain as follows：With
Hydrothermal synthesis method synthesis metallic organic framework porous material MIL-53 (Al), first, weighs Al (NO3) 3.9H2O of 5.2g, to
It adds the deionized water of 20mL, and stirring makes it dissolve；Then weigh the terephthalic acid (TPA) of 1.152g, be slowly added to Al (NO3)
In 3.9H2O solution, magnetic agitation 30min, then solution is transferred to in teflon-lined autoclave,
Put in 220 DEG C of drying box, crystallization 96h, after reaction terminates, naturally cool to room temperature, centrifugation, washing, vacuum is done
Dry 10h, obtains white metal organic backbone porous material MIL-53 (Al).
Embodiment 9, this support type catalyst without mercury is obtained by following preparation methods：The first step, weighs 0.84g Bi (NO3)
In 3 deionized waters dissolving in 10mL, dropwise drip dilute HNO3 to Bi (NO3) 3 and be completely dissolved, the presoma obtaining Bi after dissolving is molten
Liquid；Second step, weighs 1.80g metallic organic framework porous material MIL-53 (Al), by metallic organic framework porous material MIL-
53 (Al) adds in the precursor solution of Bi, stirring dipping 24h, 10h is dried after dipping at temperature is 100 DEG C, after being dried
Nitrogen protection under temperature be 350 DEG C at roasting 4h, N2 pressure be 0.01MPa, through compressing tablet after roasting, obtain support type mercury-free and urge
Agent.In the support type catalyst without mercury that embodiment 9 obtains, the percent mass load capacity of Bi is 20%.
In embodiment 9, metallic organic framework porous material MIL-53 (Al) can be commercially available, also can have by metal in embodiment 8
The preparation method of machine skeletal porous material MIL-53 (Al) obtains.
Embodiment 10, this support type catalyst without mercury is obtained by following preparation methods：The first step, weighs 20.9mg
HAuCl4 4H2O, uses acetonitrile (about 3mL) to dissolve, obtains the precursor solution of Au after dissolving under room temperature；Second step, weighs
0.76g metallic organic framework porous material MOF-5, metallic organic framework porous material MOF-5 is added the precursor solution of Au
In, ultrasonication 30min, stand 12h, 6h is dried at temperature is 100 DEG C after standing, under nitrogen protection in temperature after being dried
Spend for roasting 4h at 120 DEG C, N2 pressure is 0.01MPa, through compressing tablet after roasting, obtains support type catalyst without mercury.Embodiment 10
In the support type catalyst without mercury obtaining, the percent mass load capacity of Au is 0.5%.
In embodiment 10, metallic organic framework porous material MOF-5 can be commercially available, also can obtain as follows：Weigh
The terephthalic acid (TPA) of Zn (NO3) 2 6H2O and 0.66g of 3.60g, is dissolved in the DMF of 50mL, magnetic stirrer
Then solution be transferred to in teflon-lined autoclave, putting in 80 DEG C of drying box, crystallization by 30min
Reaction 24h, is then slowly cooled to room temperature, mixed liquor centrifugation, obtains white solid particle, i.e. metallic organic framework porous
Material MOF-5.
Embodiment 11, this support type catalyst without mercury is obtained by following preparation methods：The first step, weighs 41.8mg
HAuCl4 4H2O, uses acetonitrile (about 3mL) to dissolve, obtains the precursor solution of Au after dissolving under room temperature；Second step, weighs
2.00g metallic organic framework porous material MOF-5, this porous material MOF-5 is added in the precursor solution of Au, at ultrasonic wave
Reason 30min, stands 12h, 6h is dried after standing at temperature is 100 DEG C, after being dried under nitrogen protection at temperature is 120 DEG C
Roasting 6h, N2 pressure is 0.01MPa, through compressing tablet after roasting, obtains support type catalyst without mercury.The support type that embodiment 11 obtains
In catalyst without mercury, the percent mass load capacity of Au is 1%.
In embodiment 11, metallic organic framework porous material MOF-5 can be commercially available, also can be organic by metal in embodiment 10
The preparation method of skeletal porous material MOF-5 obtains.
Embodiment 12, this support type catalyst without mercury is obtained by following preparation methods：The first step, weighs 1.06g Co
(NO3) 3.6H2O dissolves in the precursor solution obtaining Co in the deionized water of 10mL after dissolving；Second step, weighs 2.00g metal
Organic backbone porous material MIL-53 (Al), metallic organic framework porous material MIL-53 (Al) is added the precursor solution of Co
In, stirring dipping 24h, 12h is dried at temperature is 120 DEG C after dipping, after being dried under nitrogen protection at temperature is 350 DEG C
Roasting 4h, N2 pressure is 0.01MPa, through compressing tablet after roasting, obtains support type catalyst without mercury.The support type that embodiment 12 obtains
In catalyst without mercury, the percent mass load capacity of Co is 10%.
In embodiment 12, metallic organic framework porous material MIL-53 (Al) can be commercially available, also can be by metal in embodiment 8
The preparation method of organic backbone porous material MIL-53 (Al) obtains.
Embodiment 13, this support type catalyst without mercury is obtained by following preparation methods：The first step, weighs 106.24mg
H2PtCl6 6H2O, under room temperature, deionized water (about 3mL) dissolving, obtains the precursor solution of Pt after dissolving；Second step, claims
Take 2.00g metallic organic framework porous material MOF-5, will be molten for the presoma of metallic organic framework porous material MOF-5 addition Pt
In liquid, ultrasonication 30min, stand 12h, 6h is dried at temperature is 100 DEG C after standing, exists under nitrogen protection after being dried
Temperature is roasting 8h at 120 DEG C, and N2 pressure is 0.01MPa, through compressing tablet after roasting, obtains support type catalyst without mercury.Embodiment
In the support type catalyst without mercury that 13 obtain, the percent mass load capacity of Pt is 2%.
In embodiment 13, metallic organic framework porous material MOF-5 can be commercially available, also can be organic by metal in embodiment 10
The preparation method of skeletal porous material MOF-5 obtains.
Embodiment 14, this support type catalyst without mercury application in preparing chloroethylene by acetylene hydrochlorination.
Application in preparing chloroethylene by acetylene hydrochlorination for the support type catalyst without mercury that above-described embodiment is obtained, test
As follows, test data is shown in Table 1.
1. the support type catalyst without mercury that embodiment 5 obtains, for preparing vinyl chloride by hydrochlorination of acetylene monomer, in reality
Test under the process conditions of room, the conversion ratio of acetylene is 18.37%, and after reaction 400min, support type catalyst without mercury of the present invention
Activity remain above under identical space velocities the activity of industrial mercury catalyst, selectively suitable with industry mercury catalyst.
2. the support type catalyst without mercury that embodiment 6 obtains, for preparing vinyl chloride by hydrochlorination of acetylene monomer, in reality
Test under the process conditions of room, the conversion ratio of acetylene is 15.36%, and after reaction 500min, support type catalyst without mercury of the present invention
Activity remain above under identical space velocities the activity of industrial mercury catalyst, selectively suitable with industry mercury catalyst.
3. the support type catalyst without mercury that embodiment 7 obtains, for preparing vinyl chloride by hydrochlorination of acetylene monomer, in reality
Test under the process conditions of room, the conversion ratio of acetylene is 13.41%, and after reaction 300min, support type catalyst without mercury of the present invention
Activity remain above under identical space velocities the activity of industrial mercury catalyst, selectively suitable with industry mercury catalyst.
4. the support type catalyst without mercury that embodiment 8 obtains, for preparing vinyl chloride by hydrochlorination of acetylene monomer, in reality
Test under the process conditions of room, the conversion ratio of acetylene is 9.64%, and after reaction 180min, the activity of support type catalyst without mercury does not have
There is obvious reduction, selectively suitable with industrial mercury catalyst.
5. the support type catalyst without mercury that embodiment 9 obtains, for preparing vinyl chloride by hydrochlorination of acetylene monomer, tests
Under the process conditions of room, the conversion ratio of acetylene is 9.32%, and after reaction 180min, the activity of support type catalyst without mercury does not have
Significantly reduce, selectively suitable with industrial mercury catalyst.
6. the support type catalyst without mercury that embodiment 10 obtains, for preparing vinyl chloride by hydrochlorination of acetylene monomer,
Under the conditions of laboratory process, the conversion ratio of acetylene is 9.54%, selectively suitable with industrial mercury catalyst.
7. the support type catalyst without mercury that embodiment 11 obtains, for preparing vinyl chloride by hydrochlorination of acetylene monomer,
Under the conditions of laboratory process, the conversion ratio of acetylene is 14.90%, is used for acetylene hydrochlorination higher than existing industry mercury catalyst and reacts
Prepare the conversion ratio of acetylene in VCM.
8. the support type catalyst without mercury that embodiment 12 obtains, for preparing vinyl chloride by hydrochlorination of acetylene monomer,
Under the conditions of laboratory process, the conversion ratio of acetylene is 11.16%, is used for acetylene hydrochlorination higher than existing industry mercury catalyst and reacts
Prepare the conversion ratio of acetylene in VCM.
9. the support type catalyst without mercury that embodiment 13 obtains, for preparing vinyl chloride by hydrochlorination of acetylene monomer,
Under the conditions of laboratory process, the conversion ratio of acetylene is 10.33%, is used for acetylene hydrochlorination close to existing industry mercury catalyst anti-
The conversion ratio of acetylene in VCM should be prepared.
In sum, the present invention by equi-volume impregnating or crosses volume impregnation method that active component is supported on metal is organic
On skeletal porous material, obtain the support type catalyst without mercury of environmental protection, support type catalyst without mercury good stability of the present invention,
Under identical process conditions, the activity and selectivity of support type catalyst without mercury of the present invention is higher than or is catalyzed with existing industry mercury
Agent is suitable；Meanwhile, present invention firstly provides the support type catalyst without mercury prepared for carrier of metallic organic framework porous material
Application in preparing chloroethylene by acetylene hydrochlorination, can variation, produce VCM to environmental protection, greatly reduce
Industrial mercury catalyst is to the pollution of environment and potential safety hazard.
Above technical characteristic constitutes embodiments of the invention, and it has stronger adaptability and implementation result, can basis
It is actually needed the non-essential technical characteristic of increase and decrease, to meet the demand of different situations.
Table 1
Note：Laboratory process condition is：V(HCl)：V(C2H2)=1.05, acetylene air speed is 331h-1, 170 DEG C, normal pressure；
Measure process conditions during industrial mercury catalyst activity：V(HCl)：V(C2H2)=1.05, acetylene air speed is 331h-1, 140 DEG C,
Normal pressure.
Claims (9)
1. a kind of support type catalyst without mercury is it is characterised in that obtain as follows：The first step, by the chloride of active component
Or obtain activearm after the phosphate solvent dissolving of the nitrate of active component or the sulfate of active component or active component
The precursor solution dividing；Metallic organic framework porous material is added by second step by equi-volume impregnating or excessively volume impregnation method
Impregnated in the precursor solution of active component, after dipping after drying, the lower roasting of nitrogen protection and compressing tablet, loaded
Type catalyst without mercury.
2. support type catalyst without mercury according to claim 1 is it is characterised in that active component is Bi or Cu or Sn or Co
Or Au or Pd or Pt or Ru or Ir or therein more than one；Or/and, the quality hundred of active component in support type catalyst without mercury
Load capacity is divided to be 0.5% to 30%.
3. support type catalyst without mercury according to claim 1 and 2 is it is characterised in that solvent is deionized water or acetonitrile；
Or/and, the precursor solution of metallic organic framework porous material and active component is 1 by volume:1 to 1:3 mixing.
4. the support type catalyst without mercury according to claim 1 or 2 or 3 is it is characterised in that baking temperature is 90 DEG C to 110
DEG C, drying time is 10h to 24h；Or/and, sintering temperature is 120 DEG C to 350 DEG C, and roasting time is 2h to 8h；Or/and, N2
Pressure is 0.01MPa to 0.2MPa.
5. a kind of preparation method of support type catalyst without mercury is it is characterised in that carry out in the steps below：The first step, by activearm
After the chloride dividing or the solvent dissolving of the phosphate of the nitrate of active component or the sulfate of active component or active component
Obtain the precursor solution of active component；Second step is many by metallic organic framework by equi-volume impregnating or volume impregnation method excessively
Porous materials are added in the precursor solution of active component and are impregnated, through drying, the lower roasting of nitrogen protection and compressing tablet after dipping
Afterwards, obtain support type catalyst without mercury.
6. support type catalyst without mercury according to claim 5 preparation method it is characterised in that active component be Bi or
Cu or Sn or Co or Au or Pd or Pt or Ru or Ir or therein more than one；Or/and, activearm in support type catalyst without mercury
The percent mass load capacity divided is 0.5% to 30%.
7. the preparation method of the support type catalyst without mercury according to claim 5 or 6 is it is characterised in that solvent is deionization
Water or acetonitrile；Or/and, the precursor solution of metallic organic framework porous material and active component is 1 by volume:1 to 1:3 mix
Close.
8. the preparation method of the support type catalyst without mercury according to claim 5 or 6 or 7 is it is characterised in that baking temperature
For 90 DEG C to 110 DEG C, drying time is 10h to 24h；Or/and, sintering temperature is 120 DEG C to 350 DEG C, and roasting time is for 2h extremely
8h；Or/and, N2Pressure is 0.01MPa to 0.2MPa.
9. a kind of support type catalyst without mercury according to claim 1 or 2 or 3 or 4 is in preparing chloroethylene by acetylene hydrochlorination
In application.
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