CN106460093B - The manufacture method of nickel silicon alloy - Google Patents
The manufacture method of nickel silicon alloy Download PDFInfo
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- CN106460093B CN106460093B CN201580025843.XA CN201580025843A CN106460093B CN 106460093 B CN106460093 B CN 106460093B CN 201580025843 A CN201580025843 A CN 201580025843A CN 106460093 B CN106460093 B CN 106460093B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J25/00—Catalysts of the Raney type
- B01J25/02—Raney nickel
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J25/00—Catalysts of the Raney type
- B01J25/04—Regeneration or reactivation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/02—Heat treatment
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/08—Alloys with open or closed pores
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
- C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C31/02—Monohydroxylic acyclic alcohols
- C07C31/125—Monohydroxylic acyclic alcohols containing five to twenty-two carbon atoms
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The present invention provides a kind of method that used nisiloy system sponge catalysts are used as into a part for raw material and manufacture nickel silicon alloy, and its main composition is：Nickel source comprising used sponge nickel catalyst, silicon source and carbon source are supplied in electric furnace, 4 hours to 30 hours heating responses are carried out at being 1,200 DEG C to 1,500 DEG C in the in-furnace temperature of electric furnace.New nickel, used sponge nickel catalyst, the mixture of electric furnace remaining nickel silicon alloy semi-products can be used in nickel source, and the material for being mixed into metallic silicon and being formed in silica can be used in silicon source, and commercially available charcoal or sawdust charcoal can be used in carbon source.Most preferably 1,230 DEG C to 1,270 DEG C of the in-furnace temperature of electric furnace.
Description
Technical field
The present invention relates to it is a kind of using as the used dead catalyst of the sponge nickel catalyst of hydrogenation catalyst as
Raw material and the method for manufacturing nickel-silicon alloy.
Background technology
Sponge Ni hydrogenation catalysts are the catalyst that Mo Lileini (Muray Raney) is invented, generally to be used as commodity
The address of the Raney's nickel (Raney Nickel) of name is big well known, such as institute in 1,628, No. 190 specifications of U.S. Patent No.
Record, it is the alloy for producing metal and the metal without catalyst action with catalyst action, and will not had
The metal of catalyst action utilizes the alkaline aqueous solution metal that partly dissolution removes (referred to as " deploying the operation ") and obtained
Catalyst.
Mo Lileini (Muray Raney) also studied the ternary system that silicon is added in addition to the combination of nickel and aluminium.If
Using silicon, the mixture of aluminium, then because the character of two metals is different, so alloy manufacture becomes complicated.Therefore, only all the time
Alloy is manufactured by nickel and aluminium.
At present, in the market sold, usually used sponge Ni hydrogenation catalysts be the sponge nickel of nickel-aluminum system.
In atmosphere then can spontaneous combustion in addition, if used nickel-aluminum system sponge nickel catalyst is placed, it is therefore necessary to
Preserve in water, and discard after the deactivation for a long time, in view of this problem, it may be said that be extremely difficult by used nickel-aluminum system sponge
Raney nickel is further used as catalyst, but from the price of nickel is high and utilization of resources from the viewpoint of, actual conditions be
The recycling (regeneration) on the catalyst has been carried out many research in the art.
For example, the inventor Mo Lileini (Muray Raney) of sponge catalysts it is also proposed used catalysis
Agent is regenerated as the method (patent document 2) of alloy.This method is to aoxidize used sponge nickel catalyst and be made
Oxide, reducing substances is mixed in the oxide and is heated and manufactures alloy.
In addition, known following method in addition：Raney's nickel is used in the hydrogenative decomposition of organic peroxide polymer
(nickel-aluminum system sponge) catalyst, implement batch reaction, the catalyst inactivated every time is separated after the reaction, catalyst is existed
Deploy regeneration in alkaline aqueous solution, so as to be recycled (patent document 3).
Prior art literature
Patent document
Patent document 1：No. 2,139,602 specifications of U.S. Patent No.
Patent document 2：Japan Patent examined patent publication 53-38719 publications
Non-patent literature
Non-patent literature 1：Hydrogenation, page 25~page 59, RL, L Austria in fine chemistry industry (Fine Chemical)
Marquis de Custine (RL, LAuguestine) is write, upper former mound one is translated, daily magazine industry publishing house (in March, 1974)
Non-patent literature 2：Contact hydrogenation, page 15~page 21, Xi Cun weights husband, high wooden string write, Tokyo chemistry it is same
People's (in April, 1987)
The content of the invention
Invent problem to be solved
However, the process length of method described in patent document 1, cost of equipment or regeneration cost uprise, and in industry
It is upper not utilized.
In addition, method described in patent document 2 is to utilize specific phenomenon in hydrogenative decomposition, exists and ask as follows
Topic：Even if implementing the recycling of the catalyst used in the hydrogenation of double bond using same method, it can not also recover catalyst
Function.
In a word, industrially in beneficial method, in the past and it is unaware of using used nickel-silicon system sponge catalysts
The method made a part for raw material and manufacture nickel-silicon alloy.
The technological means solved the problems, such as
The present invention is in view of the problem of the prior art, there is provided it is a kind of conventional and it is unenforced by used nickel-
The method that silicon systems sponge catalysts are used as a part for raw material and manufacture nickel-silicon alloy.
This method can also be used in other metallic catalysts, copper, iron, cobalt, chromium etc. that sponge catalysts can also be used beyond nickel
Make catalyst.In addition, as the metal without catalyst action, i.e. removed using alkali, in addition to silicon, can also be used
Aluminium, arsenic, zinc, magnesium etc..
As described above, Mo Lileini (Muray Raney) proposes the trial that alloy is only manufactured by nickel and aluminium, but the present invention
Aluminium is removed and manufactured the alloy formed by nickel and silicon in the composition by person et al., evaluates its hydrogenation catalyst work(to double bond
Can, as a result discovery is almost equal with nickel-aluminum system, so as to complete the present invention.
That is, according to the present invention, there is provided a kind of manufacture method of nickel-silicon alloy, used sponge nickel will be included and be catalyzed
Nickel source, silicon source and the carbon source of agent are supplied in electric furnace, are carried out 4 hours at being 1,200 DEG C to 1,500 DEG C in the in-furnace temperature of electric furnace
To 30 hours heating responses.
In addition, according to the present invention, there is provided the manufacture method of the nickel-silicon alloy, wherein nickel source be selected from by new nickel, made
It is more than one or both of group that used sponge nickel catalyst, electric furnace remaining nickel-silicon alloy semi-products are formed mixed
Compound.
In addition, according to the present invention, there is provided the manufacture method of the nickel-silicon alloy, wherein silicon source are metallic silicon and/or silicon
Stone.
In addition, according to the present invention, there is provided the manufacture method of the nickel-silicon alloy, wherein carbon source for commercially available charcoal and/or
Sawdust charcoal.
In addition, according to the present invention, there is provided the manufacture method of the nickel-silicon alloy, the wherein in-furnace temperature of electric furnace are 1,230
DEG C to 1,270 DEG C.
In addition, according to the present invention, there is provided the manufacture method of the nickel-silicon alloy, wherein used sponge nickel is catalyzed
In agent, nickel purity is 50 weight % to 70 weight %, and silicon is 30 weight % to 50 weight %, and iron is below 4 weight %.
In addition, according to the present invention, there is provided the manufacture method of the nickel-silicon alloy, wherein the purity of the new nickel as nickel source
For more than 99.5 weight %.
In addition, according to the present invention, there is provided the manufacture method of the nickel-silicon alloy, wherein the purity of the silica as silicon source
For more than 99.0 weight %.
In addition, according to the present invention, there is provided the manufacture method of the nickel-silicon alloy, wherein the metallic silicon as silicon source is pure
Spend for more than 99.0 weight %.
In addition, according to the present invention, there is provided the manufacture method of the nickel-silicon alloy, wherein charcoal or sawdust as carbon source
Charcoal not sulfur-bearing, phosphorus, arsenic, bismuth, halogen.
In addition, according to the present invention, there is provided the manufacture method of the nickel-silicon alloy, wherein raw material is advanced with into mixer
It is supplied to after homogeneous mixing in electric furnace.
In addition, according to the present invention, there is provided the manufacture method of the nickel-silicon alloy, wherein the height obtained using frit reaction
It is 4.3 to 5.1 that the nickel-silicon stone alloy of temperature, which places the proportion after cooling, and contains the weight % of nickel 45 to 65 weight %, the weight of silicon 35
Measure % to 50 weight %, below the weight % of iron 4.
In addition, according to the present invention, there is provided the manufacture method of the nickel-silicon alloy, wherein individually or repeating following work
Sequence：The 80 weight % used sponge nickel catalysts used above of nickel source and manufacture nickel-silicon alloy.
The effect of invention
By using the method for the present invention, the used nickel-silicon system sponge nickel that can not will can be recycled so far
Catalyst is as raw material, the nickel-silicon alloy of a large amount of and qurer manufacture nickel-silicon system sponge nickel catalyst.
On the effect, if used nickel-silicon system sponge nickel catalyst placed in atmosphere can spontaneous combustion, because
This must be preserved in water for a long time, and be discarded after the deactivation, in view of the common technical knowledge of this art, according to the present invention,
Used nickel-silicon system sponge nickel catalyst can be recycled, and can ensure that its security, it is also notable in terms of environment
It is excellent.
Brief description of the drawings
Fig. 1 is the skeleton diagram of the manufacturing process of the nickel-silicon alloy in the present invention.
Fig. 2 is the skeleton diagram of the hydrogenation apparatus in the present invention.
Drawing reference numeral explanation：
1：Mixer；
2：Container；
3：Raw material stores disk；
4：Carbon electrode；
5：Electric arc furnaces；
6：Connect disk；
7：No.1 precipitrons；
8：No.2 precipitrons；
9：Container bag；
10：No.1 hair-dryers；
11：No.2 hair-dryers；
12：Feed pump；
13：Hydrogenator；
14：Circulating pump.
Embodiment
Hereinafter, according to embodiment, the present invention will be described in detail.
The invention reside in a kind of silica carbon reduction method, and it is used as that used nickel-silicon system sponge nickel catalyst can be entered
Row is recycled and the method for a large amount of and qurer manufacture nickel-silicon alloy, and silica is reduced using carbon in electric furnace and is converted
For silicon, make the silicon and nickel reactant.
That is, metallic nickel is reacted and the conjunction of manufacturing objective nickel-silicon with the silicon generated in following (1) formulas as (2) formula
The method of gold.
＜ reaction equations ＞
Silica is reacted with carbon as (1) formula, and silica is reduced into silicon, and the silicon is carried out instead with nickel as (2) formula
Answer and form nickel-silicon alloy.
SiO2+2C→Si+2CO······(1)
xNi+ySi→(Ni)x(Si)y······(2)
SiO2：Silica C：Carbon Si：Silicon CO：Carbon monoxide
The used nickel-silicon system sponge nickel used in new nickel, hydrogenation etc. can be used alone or as a mixture in nickel source
Caused electric furnace remaining nickel-silicon alloy semi-products (hereinafter referred to as electric furnace remaining alloy half in catalyst, alloy manufacturing process
Product) etc..
Particularly, in the case where used nickel-silicon system sponge nickel catalyst is used as into nickel source, even if with 80 weights
Amount more than % ratio is mixed into raw material, can also be reused.The warp that can be recycled with such a height ratio
Advantage (merit) in Ji is big.
Silicon source uses silica (SiO2), use charcoal or sawdust charcoal silica to be reduced to the carbon source of silicon (Si).Foundation
(1) formula, silicon is obtained using the reaction of silica and carbon, the silicon is reacted according to (2) formula with nickel and obtains nickel-silicon alloy, silicon source
Also silicon can be mixed into silica in itself and used.
The electrolytic nickel of the preferred high-purity of new nickel as nickel source, specifically, its purity are preferably more than 99.5 weight %.
Also the change of the element comprising sulphur, phosphorus, arsenic, bismuth etc. with lone electron pair containing below 0.5 weight % in new nickel
Compound is preferably free of halide ion and organohalogen compound as impurity.
The reason is that nickel-silicon alloy deploys in alkaline aqueous solution, sponge nickel catalyst is prepared, is mainly used in double bond
The hydrogenation of (carbon-carbon bond or carbon-oxygen bond in compound etc.), but due to the nickel metal raw of the active site as sponge nickel catalyst
Son has empty d- tracks, so there is the compound of lone electron to be coordinated on nickel for these, it will be apparent that played as catalyst poison
Effect.
React with active nickel metallic atom in addition, halogen and organohalogen compound also have and catalyst function is reduced it
Anxiety, particularly, iodine compound can significantly reduce activity.
In addition, as the used nickel-silicon system sponge nickel catalyst used in other nickel sources, hydrogenation etc.,
Caused electric furnace remaining nickel-silicon alloy semi-products etc. are due to without above-mentioned impurity in alloy manufacturing process, so can directly use
Make raw material.
(analysis method)
Nickel purity：It is pure according to Japanese Industrial Standards (Japanese Industrial Standards, JIS) H 1,151 2.
Divide (Ni+Co) quantitative approach.
Sulphur：According to the hydrogen sulfide vaporization separation methylene blue absorption photometrys of JIS H 1,151 12.2.Detectable limit：
0.0001 weight %
Phosphorus：According to the phosphorus quantitative approach in the nickel of JIS H 1278 and nickel alloy.Detectable limit：0.0005 weight %
Arsenic：According to the arsenic trichloride separated molybdenum arsenic acid indigo plant absorption spectrophotometries of JIS G 1225.Detectable limit：0.0005 weight
Measure %
Bismuth：According to the bismuth quantitative approach in the nickel of JIS H 1272 and nickel alloy.Detectable limit：0.001 weight %
Halogen and organic halogen：According to sample combustion ion chromatography (ion chromatography).Detectable limit：10
Weight ppm
The preferred purity of silica as raw material is more than 99.0 weight %, in the case of containing impurity, may be allowed 0.1 weight
Measure below % calcium oxide, below 0.2 weight % aluminum oxide, below 0.1 weight % magnesia.
If containing the impurity more than content, these compounds as with alkali silica reaction and generate salt alkali play
Act on and generate the indissoluble salt of silica, therefore the reduction using carbon of silica can be hindered.In addition, closed using not phosphorous and vulcanization
The silica of thing.The reason is that phosphorus and sulphur compound turn into catalyst poison when as hydrogenation catalyst.
(analysis method)
Silica purity：According to JIS M 8852：1998 8.3 dehydrated weights analysis photometric analysis of extinction and usage.Detection
The limit：0.1 weight %
Calcium oxide：According to JIS M 8852：1998 13 inductively coupled plasmas (Inductively Coupled
Plasma, ICP) luminescence analysis.Detectable limit：0.005 weight %
Aluminum oxide：According to JIS M 8852：1998 9 ICP luminescence analysis.Detectable limit：0.02 weight %
Magnesia：According to JIS M 8852：1998 14 ICP luminescence analysis.Detectable limit：0.002 weight %
The preferred purity of metallic silicon as raw material is more than 99.0 weight %.In addition, it may be allowed the weight of iron 0.5 as impurity
Measure below %, below the weight % of aluminium 0.5, below the weight % of calcium 0.3, but preferably not phosphorous and boron.
(analysis method)
Silicon metal purity：According to JIS G 1322-1：2010 silicon quantitative approach gravimetric methods.Detectable limit：0.1 weight %
Iron：According to JIS G 1322-5：2010 silicon separate ICP luminescence analysis.Detectable limit：0.001 weight %
Aluminium：According to JIS G 1322-6：2010 silicon separate ICP luminescence analysis.Detectable limit：0.001 weight %
Calcium：According to JIS G 1322-7：2010 silicon separate ICP luminescence analysis.Detectable limit：0.001 weight %
Phosphorus：According to JIS G 1322-3：2010 6. silicon separate ICP luminescence analysis.Detectable limit：0.002 weight %
Boron：According to JIS G 1322-3：2010 6. silicon separate ICP luminescence analysis.Detectable limit：1 weight ppm
Carbon source used in the reduction of silica uses commercially available charcoal and/or sawdust charcoal etc., but preferably using without use
When making hydrogenation catalyst as the sulphur of catalyst poison, phosphorus, arsenic, bismuth, halogen material.
(analysis method)
Sulphur：According to sample combustion ion chromatography.
Detectable limit：10 weight ppm
Phosphorus：According to ICP luminescence analysis.Detectable limit：1 weight ppm
Arsenic：According to ICP luminescence analysis.Detectable limit：1 weight ppm
Bismuth：According to ICP luminescence analysis.Detectable limit：1 weight ppm
Halogen and organic halogen：According to sample combustion ion chromatography.Detectable limit：10 weight ppm
Can freely it be adjusted by the allotment of raw material using the nickel of the nickel-silicon alloy manufactured by electric furnace and the ratio of silicon.
But after being deployed using alkaline aqueous solution, the requirement of its catalyst function and mechanical strength during according to as hydrogenation catalyst,
Must be so that the weight % of the weight % of proportion 4.3~5.1, the weight % of nickel 45~65, the weight % of silicon 35~50, the weight % of iron 4 can be obtained
The mode of following nickel-silicon alloy is adjusted.
If the nickel in alloy ratio increase and turn into more than the weight % of nickel 65, below the weight % of silicon 35, proportion into
For more than 5.1, become difficult using the expansion of alkaline aqueous solution, the activity as hydrogenation catalyst reduces., whereas if silicon increases
Add and turn into below the weight % of nickel 45, more than the weight % of silicon 50, then proportion turns into less than 4.3, becomes fragile and is utilizing alkalescence water-soluble
Catalyst is not used as after liquid expansion.
In order to manufacture the alloy of the target composition, it is necessary to adjust and used according to the species of the nickel used in raw material
The suitable weight of silicon and carbon ratio.
Table 1. is according to the nickel source supplied, the ratio of the suitable weight of required silicon and carbon
Actually use three kinds of nickel sources, therefore based on 1)~3) ratio addition silicon source and carbon, be used as upon mixing
Raw material.
The preferred nickel purity of used sponge nickel catalyst that can be used as raw material is 50 weight % is to 70 weight %, silicon
30 weight % to 50 weight %, iron are below 4 weight %.
(analysis method)
Proportion：JIS Z 8807：2012
In the present invention, electric furnace, preferably electric arc furnaces are used in order to manufacture nickel-silicon alloy.
(disposal of the thick alloy of extraction)
The thick alloy of extraction is directly placed at into product to connect disk and cooled down.After cooling, from the upper layer part three for connecing disk
Position is sampled, and determines its proportion.It is averaged the semifinished product proportion that value is set to the extraction batch.
(analysis method)
Proportion：According to JIS Z 8807：2012 utilize the density of weighing method and the assay method of proportion in liquid.
(preparation as the sponge nickel of hydrogenation catalyst)
As the maximum purposes of nickel-silicon alloy manufactured in the present invention sponge nickel preparation method in lot of documents (example
Such as, non-patent literature 1, non-patent literature 2) in it is on the books.In general, nickel-silicon alloy is deployed in alkaline aqueous solution, and
After being washed, the sponge nickel that can be used as hydrogenation catalyst is obtained.
(prepared by sponge nickel catalyst：Expansion)
If represent that sponge nickel catalyst prepares one of method, as described below.
It is in 48% hydrogen by nickel-silicon alloy that diameter 25mm~6mm fixed bed hydrogenation units, which are prepared, with the method for sponge nickel
After deploying in sodium hydroxide solution with 85 DEG C, 45 minutes 2 hours, room temperature is cooled to, wash within more than 8 hours, hydrogenation is obtained and uses
Sponge nickel.The nickel content of the sponge nickel so obtained is the weight % of 50 weight %~70, and silicone content is the weight of 50 weight %~30
Measure %.
(analysis method)
Nickel：According to silicon separation dimethyl glyoxime gravimetric method.Detectable limit：0.1 weight %
Silicon：According to JIS G 1322-1：2010 silicon quantitative approach gravimetric methods.Detectable limit：0.1 weight %
(processing of the sponge nickel catalyst after expansion)
If the fixed bed sponge nickel and air contact of the acquisition, can be aoxidized, heat release and inactivate.Separately
Outside, its process is oxidation → dryings → heat release → on fire, therefore makes the situation of the catalyst after alloy expansion and air contact non-
It is often dangerous.Also aoxidized in the state of moistening, but inactivation will not be caused within 10 minutes.
(nickel-silicon alloy manufacturing flow chart)
The outline for the flow chart (flow sheet) that machine in the nickel-silicon alloy manufacture of the present invention is set is shown in Fig. 1.
In Fig. 1, illustration uses situation of the electric arc furnaces as electric furnace.
Fig. 1 nickel-silicon alloy manufacturing process skeleton diagram is illustrated.
After the raw material of ormal weight is sufficiently mixed in mixer 1, it is stored in container (container) 2.It must utilize
The advance homogeneous of raw material is mixed backward electric furnace and supplied by mixer.If the reason is that undercompounding, the silicon as silicon source
Stone fully can not be reduced to silicon and directly be remained in the form of insoluble silica in electric arc furnaces using carbon source.It can turn into resistance
Hinder the factor continuously run.
Secondly, the sequence of operation according to electric furnace, completes the preparation of stove.After the preparation for completing stove, according to startup (start
Up) order, by the running warm of stove to usual operating temperature (1,200 DEG C~1,500 DEG C).In operating, the temperature in stove is protected
Hold the scope for 1,200 DEG C~1,400 DEG C, more preferably 1,230 DEG C~1,270 DEG C.If reach the shape that can continue generally to operate
State, then the raw material being adequately mixed of container 2 is moved on into raw material storage disk 3, necessary amount is put into by electric arc furnaces with fixing speed
5, so as to manufacture alloy.Make the in stable condition needs 1 hour~2 hours in electric arc furnaces, it is small further to carry out 4 hours~30 thereafter
When heating response, turn into can steady production nickel-silicon alloy state.
Target nickel-silicon alloy is to extract to connect disk 6 at intervals of set time.When the alloy for connecing the extraction of disk 6 is cooled into room
Wen Shi, it is crushed using disintegrating machine (crusher), be classified as the size (size) corresponding to application target thereafter, obtain
Obtain the nickel-silicon alloy product of size uniform.Caused dust is dried using No.1 hair-dryers (blower) 10, No.2 in operation
Machine 11 aspirates, and is removed using No.1 precipitrons 7 and No.2 precipitrons 8.The dirt of dust is to be accommodated in container bag (flexible
Container) handled in 9.
The hydrogenation apparatus skeleton diagram of the present invention is represented in Fig. 2.
In fig. 2, using feed pump (feed pump) 12 to provide flow continuous feed raw material aldehyde (aldehyde).To
Deployed sponge nickel catalyst (a diameter of 25mm~6mm) is pre-charged with hydrogenator 13 with refrigerating function.Secondly, profit
The reaction solution for making hydrogenator with circulating pump 14 is circulated with regulation flow.The hydrogen of authorized pressure is fed in hydrogenator and starts hydrogen
Change reaction.If reaction starts, reaction temperature rises.Reaction temperature is to keep regulation using the cooling device built in hydrogenator
Temperature.According to feed rate always self-circulating pump 14 branch line extraction equivalent hydrogenation product (alcohol).It is straight after stable reaction
Succeed continuous hydrogenation.
Embodiment
Hereinafter, based on embodiment to recovery sponge nickel related to the present invention is manufactured into nickel-silicon alloy as raw material
Method is described in detail.
(embodiment 1)
As the nickel source of raw material, relative to used sponge nickel catalyst 100kg (the weight % of nickel 62.7, silicon 34.4
Weight %, the weight % of iron 2.9), use electric furnace remaining alloy semi-products 5kg (the weight % of nickel 35.8, the weight % of silicon 61.6, iron 2.6
Weight %), new nickel 5.65kg, silicon source use charcoal 26.9kg using silica 41.1kg, carbon source, utilizes the nickel-silicon conjunction shown in Fig. 1
Described method manufacture nickel-silicon alloy in golden manufacturing flow chart.If electric furnace remaining alloy semi-products are removed, with 99%
Yield obtains proportion 4.89, the weight % of nickel 54.2, the weight % of silicon 43.4, the weight % of iron 2.3 nickel-silicon alloy product.
(embodiment 2)
As the nickel source of raw material, used sponge nickel catalyst 100kg (the weight % of nickel 62.7, the weight of silicon 34.4 are used
Measure %, the weight % of iron 2.9), in contrast, silicon source uses silica 30kg, carbon source uses charcoal 20kg, using the nickel shown in Fig. 1-
Described method manufacture nickel-silicon alloy in silicon alloy manufacturing flow chart.If removing electric furnace remaining alloy semi-products, with
99% yield obtains proportion 4.9, the weight % of nickel 55.0, the weight % of silicon 42.5, the weight % of iron 2.5 nickel-silicon alloy product.
(embodiment 3)
As the nickel source of raw material, relative to used sponge nickel catalyst 100kg (the weight % of nickel 62.7, silicon 34.4
Weight %, the weight % of iron 2.9), using new nickel 5kg, silicon source uses silica 20.6kg, metallic silicon 9.7kg, and carbon source uses charcoal
9.4kg, nickel-silicon alloy is manufactured using method described in the nickel-silicon alloy manufacturing flow chart shown in Fig. 1.If remove electricity
Stove remaining alloy semi-products, then proportion 4.9, the weight % of nickel 54.6, the weight % of silicon 43.2, the weight of iron 2.3 are obtained with 99% yield
Measure % nickel-silicon alloy product.
(embodiment 4)
As the nickel source of raw material, used sponge nickel catalyst 100kg (the weight % of nickel 62.7, the weight of silicon 34.4 are used
Measure %, the weight % of iron 2.9), in contrast, silicon source uses silica 11.6kg, metallic silicon 9.7kg, carbon source uses charcoal 4kg, profit
Nickel-silicon alloy is manufactured with method described in the nickel-silicon alloy manufacturing flow chart shown in Fig. 1.If remove electric furnace remaining to close
Golden semi-products, then with 99% yield obtain proportion 4.9, the weight % of nickel 54.5, the weight % of silicon 43.0, the weight % of iron 2.5 nickel-
Silicon alloy product.
(embodiment 5)
As the nickel source of raw material, using new nickel 100kg, in contrast, silicon source uses silica 176kg, carbon source uses charcoal
105.6kg, nickel-silicon alloy is manufactured using method described in the nickel-silicon alloy manufacturing flow chart shown in Fig. 1.If remove
Electric furnace remaining alloy semi-products, then proportion 4.9, the weight % of nickel 54.9, the weight % of silicon 45.1 nickel-silicon are obtained with 99% yield
Alloy product.
(embodiment 6)
Make embodiment 1, embodiment 2, embodiment 3, embodiment 4, the nickel-silicon alloy expansion obtained in embodiment 5 and make
Into sponge nickel-Si catalyst, the hydrogenation capacity of each sponge catalysts is determined.
First, using disintegrating machine by the nickel obtained in embodiment 1, embodiment 2, embodiment 3, embodiment 4, embodiment 5-
Silicon alloy crushes, and obtains diameter 25mm~6mm fixed bed hydrogenation alloy.
For these alloys, the method for deploying prepared using sponge nickel catalyst described in paragraph 0045 makes each alloy
Expansion, obtain sponge nickel-Si catalyst available for hydrogenation.
The measure of hydrogenation capacity is the 2.5L made using the stainless steel (stainless) shown in Fig. 2 fixed bed hydrogenation device,
Implement in the system for manufacturing 2-Ethylhexyl Alcohol using 2- ethyl hexenals as hydrogenated raw material.
Sponge nickel-the Si catalyst is to use 1L, and raw material is fed with 0.25L/Hr.Hydrogenation is to be in reaction temperature
120 DEG C~125 DEG C, reaction pressure be 2.5MPa~3.0MPa under implement.
Raw material and the hydrogenation thing obtained are analyzed using gas-chromatography (gas chromatography).
Hydrogenation is to implement 2 years.Enter promoting the circulation of qi with the hydrogenation liquid after 2 years hydrogenations of implementation when starting to reaction
Analysis of hplc, these result is summarized in table 2 and table 3.
Product analysis value (gas-chromatography %) when the hydrogenation of table 2. starts
The hydrogenation of table 3. start 2 years after product analysis value (gas-chromatography %)
Gas chromatography analysis method：Analysis machine Shimadzu GC-2014 types,
Detectable limit：0.01%
When hydrogenation starts, obtained by the alloy of embodiment 1, embodiment 2, embodiment 3, embodiment 4, embodiment 5
Sponge nickel-Si catalyst hydrogenation capacity indifference.
After hydrogenation starts 2 years, by embodiment 1, embodiment 2, embodiment 3, embodiment 4, embodiment 5 alloy
The hydrogenation capacity of sponge nickel-Si catalyst of acquisition also indifference.
According to the result of table 2, table 3, it is known that：Nickel-silicon of the used sponge nickel-Si catalyst as raw material will be used
Sponge nickel-Si catalyst obtained in the expansion of alloy (embodiment 1 to embodiment 4), the alloy (implementation with being obtained by new nickel
Example 5) expansion obtained in sponge nickel-Si catalyst when being compared, there is identical hydrogenation capacity.
(embodiment 7)
According to the method for embodiment 5, nickel-silicon alloy is manufactured using new nickel, is deployed and obtains sponge nickel catalyst.Will
It is set to catalyst A.
Reclaim catalyst A after catalyst A is used for into 2 years hydrogenations, using the method for embodiment 2 or embodiment 4 by its
It is used as the raw material of nickel-silicon alloy manufacture as used catalyst, obtains alloy, deployed and obtain sponge nickel and urge
Agent.It is set to catalyst B.
And then catalyst B is utilized into the side of embodiment 2 or embodiment 4 for reclaiming catalyst B after 2 years hydrogenations
Method obtains alloy, is deployed and obtain sea as used catalyst and as the raw material of nickel-silicon alloy manufacture
Continuous catalyst.The sponge nickel catalyst that the recycling for being repeated 4 times the catalyst is obtained is set to catalyst C.
And then catalyst C is utilized into the side of embodiment 2 or embodiment 4 for reclaiming catalyst C after 2 years hydrogenations
Method obtains alloy, is deployed and obtain sea as used catalyst and as the raw material of nickel-silicon alloy manufacture
Continuous catalyst.The sponge nickel catalyst that the recycling for being repeated 5 times the catalyst is obtained is set to catalyst D.
Using the 2.5L of the stainless steel shown in Fig. 2 fixed bed hydrogenation device, in 2- ethyl hexenals to 2-Ethylhexyl Alcohol
Hydrogenation in determine catalyst A, catalyst B, catalyst C, catalyst D hydrogenation capacity.
These sponge nickel-Si catalysts are to use 1L, and raw material is fed with 0.25L/Hr.Hydrogenation is in reaction temperature
For 120 DEG C~125 DEG C, reaction pressure be 2.5MPa~3.0MPa under implement.Raw material and the hydrogenation thing obtained are to use
Gas-chromatography is analyzed.
Hydrogenation is to implement 2 years.Enter promoting the circulation of qi with the hydrogenation liquid after 2 years hydrogenations of implementation when starting to reaction
Analysis of hplc, these result is summarized in table 4 and table 5.
Product analysis value (gas-chromatography %) when the hydrogenation of table 4. starts
The hydrogenation of table 5. start 2 years after product analysis value (gas-chromatography %)
Gas chromatography analysis method：Analysis machine Shimadzu GC-2014 types,
Detectable limit：0.01%
When hydrogenation starts, catalyst A, catalyst B, catalyst C, catalyst D sponge nickel-Si catalyst hydrogen
Change ability indifference.
After hydrogenation starts, using the catalyst A of 2 years, catalyst B, catalyst C, catalyst D sponge nickel-silicon
The hydrogenation capacity indifference of catalyst.
According to the result of table 4, table 5, it is known that：Even if being repeated 10 times following circulation (cycle), the sponge nickel obtained is catalyzed
The activity of agent is also constant, and the circulation is to manufacture nickel-silicon alloy using used sponge nickel catalyst as raw material, and should
Alloy deploys, and remanufactures sponge nickel.
(comparative example 1)
According to embodiment 7, catalyst A, catalyst B, catalyst C, catalyst D are lasted 2 years respectively and are used for 2- ethyl hexyls
The hydrogenation of olefine aldehydr, used catalyst is referred to as As, Bs, Cs, Ds.
Make these used catalyst expansion according to the catalyst method of development described in patent document 2.However,
Catalyst less producing hydrogen during expansion, being obtained only has 0.5%~1% or so weight compared to the situation before expansion
Reduce.
The hydrogenation capacity of the obtained catalyst of evaluation as described below similarly to Example 6.The measure of hydrogenation capacity is
Using the 2.5L of the stainless steel shown in Fig. 2 fixed bed hydrogenation device, manufactured using 2- ethyl hexenals as hydrogenated raw material
Implement in the system of 2-Ethylhexyl Alcohol.
Using the 0.8L sponge nickel-Si catalysts, raw material is fed with 0.20L/Hr.
Hydrogenation is implemented in the case where reaction temperature is 120 DEG C~125 DEG C, reaction pressure is 2.5MPa~3.0MPa.It is former
Material and the hydrogenation thing obtained are analyzed using gas-chromatography.
Hydrogenation liquid when starting to reaction carries out gas chromatographic analysis, and these result is summarized in into table 6.
Product analysis value (gas-chromatography %) when the hydrogenation of table 6. starts
Gas chromatography analysis method：Analysis machine Shimadzu GC-2014 types,
Detectable limit：0.01%
By by table 6 compared with the table 5 of embodiment 7, can be clear and definite：Even if used catalyst is opened up again
Open, activity does not also rise.
As a result, distinguish：Hydrogenation of the method to double bond described in patent document 2 is invalid.
Industrial utilizability
The use of the present invention industrially is carried out again using after the sponge nickel catalyst that nickel-silicon alloy manufactures
Used when raw.In addition, the sponge nickel catalyst can be used for the manufacture of following chemicals.
Positive propionic aldehyde is hydrogenated and manufactures normal propyl alcohol.
Butyl aldehyde is hydrogenated and manufactures butanol.
2- ethyl hexenals are hydrogenated and manufacture 2-Ethylhexyl Alcohol.
Benzonitrile is hydrogenated and manufactures benzylamine.
N-hexyl aldehyde is hydrogenated and manufactures n-hexyl alcohol.
Claims (13)
- A kind of 1. manufacture method of nickel-silicon alloy, it is characterised in that：By the nickel source comprising used sponge nickel catalyst, Silicon source and carbon source are supplied in electric furnace, are carried out 4 hours to 30 hours at being 1,200 DEG C to 1,500 DEG C in the in-furnace temperature of electric furnace Heating response.
- 2. the manufacture method of nickel-silicon alloy according to claim 1, wherein nickel source are selected from by new nickel, used It is more than one or both of group that sponge nickel catalyst, electric furnace remaining nickel-silicon alloy semi-products are formed.
- 3. the manufacture method of nickel-silicon alloy according to claim 1 or 2, wherein silicon source are metallic silicon and/or silica.
- 4. the manufacture method of nickel-silicon alloy according to claim 1 or 2, wherein carbon source are commercially available charcoal and/or sawdust Charcoal.
- 5. the manufacture method of nickel-silicon alloy according to claim 1 or 2, the wherein in-furnace temperature of electric furnace be 1,230 DEG C extremely 1,270℃。
- 6. the manufacture method of nickel-silicon alloy according to claim 1 or 2, wherein in used sponge nickel catalyst, Nickel purity be 50 weight % to 70 weight %, silicon be 30 weight % to 50 weight %, iron be below 4 weight %.
- 7. the manufacture method of nickel-silicon alloy according to claim 2, wherein the purity of the new nickel as nickel source is 99.5 weights Measure more than %.
- 8. the manufacture method of nickel-silicon alloy according to claim 3, wherein the purity of the silica as silicon source is 99.0 weights Measure more than %.
- 9. the manufacture method of nickel-silicon alloy according to claim 3, wherein the purity of the metallic silicon as silicon source is 99.0 More than weight %.
- 10. the manufacture method of nickel-silicon alloy according to claim 4, wherein the charcoal as carbon source or sawdust charcoal are free of Any of sulphur, phosphorus, arsenic, bismuth, halogen.
- 11. the manufacture method of nickel-silicon alloy according to claim 1 or 2, wherein raw material is advanced with into mixer homogeneous It is supplied to after mixing in electric furnace.
- 12. the manufacture method of nickel-silicon alloy according to claim 1 or 2, wherein reacting what is obtained using high-temperature fusion The proportion of nickel-silicon alloy is 4.3 to 5.1, and contains the weight % of nickel 45 to 65 weight %, the weight % of silicon 35 to 50 weight %, iron 4 Below weight %.
- 13. the manufacture method of nickel-silicon alloy according to claim 1 or 2, wherein individually or repeating following process： The 80 weight % used sponge nickel catalysts used above of nickel source and manufacture nickel-silicon alloy.
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| PCT/JP2015/065323 WO2015178499A1 (en) | 2014-05-21 | 2015-05-21 | Method for manufacturing nickel-silicon alloy |
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| JPS5453692A (en) * | 1977-10-06 | 1979-04-27 | Asahi Malleable Iron Co Ltd | Raney alloy and manufacture |
| JPS5588856A (en) * | 1978-12-27 | 1980-07-04 | Osamu Izumi | Production of nickel formed body for catalyst |
| JPS5970733A (en) * | 1982-10-18 | 1984-04-21 | Nippon Steel Corp | Reducing method of oxide of silicon or aluminum |
| CN1027044C (en) * | 1990-11-14 | 1994-12-21 | 中国石油化工总公司一坪化工厂 | Catalyst compound and its preparation |
| WO2004048621A1 (en) * | 2002-08-29 | 2004-06-10 | Elkem Asa | Production of metals and alloys using solid carbon produced from carbon-containing gas |
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| CN1326977C (en) * | 2003-08-22 | 2007-07-18 | 中国石油化工股份有限公司齐鲁分公司 | Absorbing desulfurizing catalyst for catalytic cracking petroleum and preparing method thereof |
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