A kind of green synthesis method of Cu-lyt.
Technical field
The invention belongs to the synthesis technical field of Cu-lyt., be specifically related to the green synthesis method of a kind of Cu-lyt..
Background technology
Cu-lyt. is a kind of butter, and for tetrahedral crystal shape or white cubic crystal, appearance color is white or pale powder, sometimes with loose spot shape.Cu-lyt. is slightly soluble in water, poisonous, easy photodissociation, deliquescence, is placed in air the copper chloride hydroxide (Cu being easily oxidized to green2(OH)3Cl), rapidly hydrolysis generates Cu-lyt. hydrate and white in the hot water.The more prominent position of occupation ratio in chlorine derivative product, Cu-lyt. is commonly used for catalyst in organic synthesis industry and rubber industry, such as prepare vinyl acetate with ethylene for raw material, produce a chlorobutadiene, acrylonitrile, second dialkylene acetylene etc., it is possible to prepare diphenyl ether polymerization catalyst with diamidogen;Cu-lyt. can be used as desulfurizing agent, release agent and decolorising agent in petro chemical industry;Oil and fat chemical is used as catalyst, reducing agent and flocculating agent, especially the most famous with catalyst;Except producing aniline dyes in the production of dyestuff, phthalocyanine blue, phthalocyanine green, active emerald green pigment rise outside mantoquita mating reaction, are also serving as condensing agent, catalyst and reducing agent;In silicone industry, highly active Cu-lyt. is the most important purposes of Cu-lyt. as the catalyst that methyl chloride silane mixture monomer synthesizes.High activity Cu-lyt. is the granule crystalline powder without coherent condition, its short texture, but specific surface area is big, there is small-size effect, surface and interfacial effect, quantum size effect etc., outward appearance and the physical arrangement of such Cu-lyt. are the most more complicated, because its activity is high, therefore the nanoscale Cu-lyt. synthesized by certain technique is widely used on Catalytic processes.Additionally have been widely used in metallurgical industry, electroplating industry, medical industry and agriculture chemicals fungicide industry.
The method of traditional mode of production Cu-lyt. mainly has: copper wire air oxidation process, and this method response speed is slow, material and energy expenditure height and copper wire price height and limited source;Copper sulfate method, production cost is high and reaction produces a large amount of acid mist pollution environment, and tiny being difficult to of prepared product granularity is filtered, and product easily aoxidizes;Copper scrap chlorine direct oxidation method, this method uses industrial chlorine direct oxidation, and therefore equipment anticorrosion is poor with production environmental safety;Copper scrap hydrochloric acid method, this method raw material only limits copper scrap mud, otherwise should need to add copper oxide rich in copper oxide in mud, and reaction rate is low, long action time, and product purity is the highest.
In addition, Luo Genxiang etc. prepare Cu-lyt. (CN101928034A) with copper chloride powder and copper powder for raw material in the eutectic solvent that carbamide and choline chloride are mixed to form, the method, to the dissolving of some reactants is limited and liquid temperature scope is little, limits the pure eutectic solvent range of application as reaction dissolvent.Ying Tao opens etc. and to utilize ionic liquid to prepare Cu-lyt. (CN100513315C), the method is to add the raw material in ionic liquid to react, thus reduce the pollution to environment, and can recycle after ionic liquid is separated, but because producing the problems such as garbage in ionic liquid preparation cost, biodegradability and preparation process, its green still suffers from dispute.Wang Baoluo etc. use hydrothermal reduction method to prepare Cu-lyt. (CN1235806C), the method is copper sulfate and sodium chloride to be made into mixed solution regulation acidity proceed to pressure-resistant corrosion-resistant reactor, add excess red copper powder, heating refluxes, add hydrochloric acid after reaction completely and make Cu-lyt., but the method due to the hydro-thermal method i.e. High Temperature High Pressure of feature own thus makes it have the biggest danger.Therefore exploitation a kind of simple to operate effectively, energy consumption is relatively low and eco-friendly method carrys out synthesizing chlorinated cuprous be very important.
Summary of the invention
Present invention solves the technical problem that the green synthesis method of the Cu-lyt. that there is provided a kind of simple to operate, easily controllable and environmental protection.
The present invention solves that above-mentioned technical problem adopts the following technical scheme that, a kind of green synthesis method of Cu-lyt., it is characterized in that concretely comprising the following steps: by soluble in water to solubility cupric salt and sodium acetate, under conditions of 15-25 DEG C of stirring, add reducing agent oxammonium hydrochloride. aqueous solution or oxammonium hydrochloride. solid reacts, centrifugal, washing after reaction completely, alcohol are washed and are vacuum dried and obtains target product Cu-lyt., and wherein solubility cupric salt is CuCl2·2H2O、CuBr2、Cu(NO3)2·3H2O or CuSO4·5H2O, solubility cupric salt is 1:0.1-4 with the mol ratio of oxammonium hydrochloride..
Limiting further, described sodium acetate is 1-3:1 with the mol ratio of solubility cupric salt.
The green synthesis method of Cu-lyt. of the present invention, it is characterized in that concretely comprising the following steps: by soluble in water for solubility cupric salt, react in 5-30 DEG C of addition reducing agent oxammonium hydrochloride. aqueous solution or oxammonium hydrochloride. solid, centrifugal, washing after reaction completely, alcohol are washed and are vacuum dried and obtains target product Cu-lyt., and wherein solubility cupric salt is Cu (OAc)2·H2O, solubility cupric salt is 1:0.5-5 with the mol ratio of oxammonium hydrochloride..
Limit further, the consumption of described aqueous solvent be the volume of 1mmol solubility cupric salt correspondence water be 0.5-30mL.
Limiting further, controlling stir speed (S.S.) during adding reducing agent oxammonium hydrochloride. aqueous solution or oxammonium hydrochloride. solid is 250-2000r/min, and the time adding reducing agent oxammonium hydrochloride. aqueous solution controls at 1-10min.
Limiting further, the response time that addition reducing agent oxammonium hydrochloride. aqueous solution or oxammonium hydrochloride. solid carry out reacting is 5-30min.
Limiting further, described vacuum drying temperature is 25-70 DEG C, and the vacuum drying time is 10-20h.
The present invention compared with prior art has the advantages that
1, reaction system is simple, only uses solubility cupric salt (copper source), water (solvent) and oxammonium hydrochloride. (reducing agent) during preparing target product, and they broadly fall into general chemistry reagent, cheap and easy to get;
2, reaction environment is gentle (normal temperature and pressure), and process is the most easily controllable, discharges without bazardous waste, produces for green, has the biggest environmental benefit;
3, present invention process is simple, and the response time is short, and efficiency is high, is suitable for large-scale production, has the biggest economic benefit.
Accompanying drawing explanation
Fig. 1 is the XRD figure of the Cu-lyt. that the embodiment of the present invention 1 prepares, and meets the standard diagram of the cuprous chloride crystal of JCPDS standard card 6-0344.
Detailed description of the invention
Being described in further details the foregoing of the present invention by the following examples, but this should not being interpreted as, the scope of the above-mentioned theme of the present invention is only limitted to below example, all technology realized based on foregoing of the present invention belong to the scope of the present invention.
Embodiment 1
By 0.01molCu (OAc)2·H2O is dissolved in 20mL water, drips 0.005mol oxammonium hydrochloride. aqueous solution (2mL) under the stir speed (S.S.) of 5 DEG C and 250-500r/min, and time for adding controls at 1-5min;After adding, continuing stirring 10min, centrifugal, washing, alcohol are washed, and are placed in vacuum drying oven the Cu-lyt. obtaining white in 30 DEG C of dry 20h.Product is tested through XRD, meets the standard diagram of the cuprous chloride crystal of JCPDS standard card 6-0344.
Embodiment 2
By 0.01molCu (OAc)2·H2O is dissolved in 20mL water, drips 0.005mol oxammonium hydrochloride. aqueous solution (5mL) under the stir speed (S.S.) of 25 DEG C and 1000-1500r/min, and time for adding controls at 5-10min;After adding, continuing stirring 30min, centrifugal, washing, alcohol are washed, and are placed in vacuum drying oven the Cu-lyt. obtaining white in 50 DEG C of dry 15h.Product is tested through XRD, meets the standard diagram of the cuprous chloride crystal of JCPDS standard card 6-0344.
Embodiment 3
By 0.01molCu (OAc)2·H2O is dissolved in 50mL water, drips 0.005mol oxammonium hydrochloride. aqueous solution (10mL) under the stir speed (S.S.) of 30 DEG C and 1000-1500r/min, and time for adding controls at 5-10min;After adding, continuing stirring 40min, centrifugal, washing, alcohol are washed, and are placed in vacuum drying oven the Cu-lyt. obtaining white in 50 DEG C of dry 15h.Product is tested through XRD, meets the standard diagram of the cuprous chloride crystal of JCPDS standard card 6-0344.
Embodiment 4
By 0.01molCu (OAc)2·H2O is dissolved in 100mL water, it is slowly added to 0.01mol solid hydroxylamine hydrochloride under the stir speed (S.S.) of 25 DEG C and 1500-2000r/min, continuing stirring 50min, centrifugal, washing, alcohol are washed, and are placed in vacuum drying oven the Cu-lyt. obtaining white in 50 DEG C of dry 15h.Product is tested through XRD, meets the standard diagram of the cuprous chloride crystal of JCPDS standard card 6-0344.
Embodiment 5
By 0.01molCu (OAc)2·H2O is dissolved in 250mL water, drips 0.02mol oxammonium hydrochloride. aqueous solution (3mL) under the stir speed (S.S.) of 25 DEG C and 1500-2000r/min, and time for adding controls at 5-10min;After adding, continuing stirring 40min, centrifugal, washing, alcohol are washed, and are placed in vacuum drying oven the Cu-lyt. obtaining white in 60 DEG C of dry 20h.Product is tested through XRD, meets the standard diagram of the cuprous chloride crystal of JCPDS standard card 6-0344.
Embodiment 6
By 0.01molCu (OAc)2·H2O is dissolved in 300mL water, drips 0.05mol oxammonium hydrochloride. aqueous solution (4mL) under the stir speed (S.S.) of 25 DEG C and 1500-2000r/min, and time for adding controls at 5-10min;After adding, continuing stirring 40min, centrifugal, washing, alcohol are washed, and are placed in vacuum drying oven the Cu-lyt. obtaining white in 70 DEG C of dry 20h.Product is tested through XRD, meets the standard diagram of the cuprous chloride crystal of JCPDS standard card 6-0344.
Embodiment 7
By 0.01molCuCl2·2H2O and 0.01molNaOAc is dissolved in 5mL water, drips 0.001mol oxammonium hydrochloride. aqueous solution (2mL) under the stir speed (S.S.) of 25 DEG C and 1500-2000r/min, and time for adding controls at 1-5min;After adding, continuing stirring 20min, centrifugal, washing, alcohol are washed, and are placed in vacuum drying oven the Cu-lyt. obtaining white in 70 DEG C of dry 10h.Product is tested through XRD, meets the standard diagram of the cuprous chloride crystal of JCPDS standard card 6-0344.
Embodiment 8
By 0.01molCuCl2·2H2O and 0.02molNaOAc is dissolved in 50mL water, drips 0.02mol oxammonium hydrochloride. aqueous solution (3mL) under the stir speed (S.S.) of 25 DEG C and 1500-2000r/min, and time for adding controls at 1-5min;After adding, continuing stirring 20min, centrifugal, washing, alcohol are washed, and are placed in vacuum drying oven the Cu-lyt. obtaining white in 60 DEG C of dry 20h.Product is tested through XRD, meets the standard diagram of the cuprous chloride crystal of JCPDS standard card 6-0344.
Embodiment 9
By 0.01molCuCl2·2H2O and 0.03molNaOAc is dissolved in 100mL water, drips 0.02mol oxammonium hydrochloride. aqueous solution (2mL) under the stir speed (S.S.) of 15 DEG C and 1500-2000r/min, and time for adding controls at 1-5min;After adding, continuing stirring 20min, centrifugal, washing, alcohol are washed, and are placed in vacuum drying oven the Cu-lyt. obtaining white in 70 DEG C of dry 10h.Product is tested through XRD, meets the standard diagram of the cuprous chloride crystal of JCPDS standard card 6-0344.
Embodiment 10
By 0.01molCuBr2Being dissolved in 5mL water with 0.01molNaOAc, drip 0.005mol oxammonium hydrochloride. aqueous solution (2mL) under the stir speed (S.S.) of 25 DEG C and 1500-2000r/min, time for adding controls at 1-5min;After adding, continuing stirring 20min, centrifugal, washing, alcohol are washed, and are placed in vacuum drying oven the Cu-lyt. obtaining white in 70 DEG C of dry 10h.Product is tested through XRD, meets the standard diagram of the copper chloride crystal of JCPDS standard card 6-0344.
Embodiment 11
By 0.01molCuBr2Being dissolved in 50mL water with 0.02molNaOAc, drip 0.04mol oxammonium hydrochloride. aqueous solution (2mL) under the stir speed (S.S.) of 25 DEG C and 1500-2000r/min, time for adding controls at 1-10min;After adding, continue stirring 20min, centrifugal, washing, it is placed in vacuum drying oven the Cu-lyt. obtaining white in 70 DEG C of dry 10h.Product is tested through XRD, meets the standard diagram of the copper chloride crystal of JCPDS standard card 6-0344.
Embodiment 12
By 0.01molCu (NO3)2·3H2O and 0.01molNaOAc is dissolved in 5mL water, drips 0.005mol oxammonium hydrochloride. aqueous solution (2mL) under the stir speed (S.S.) of 25 DEG C and 1500-2000r/min, and time for adding controls at 1-5min;After adding, continuing stirring 20min, centrifugal, washing, alcohol are washed, and are placed in vacuum drying oven the Cu-lyt. obtaining white in 70 DEG C of dry 10h.Product is tested through XRD, meets the standard diagram of the cuprous chloride crystal of JCPDS standard card 6-0344.
Embodiment 13
By 0.01molCu (NO3)2·3H2O and 0.03molNaOAc is dissolved in 100mL water, drips 0.02mol oxammonium hydrochloride. aqueous solution (5mL) under the stir speed (S.S.) of 15 DEG C and 1500-2000r/min, and time for adding controls at 5-10min;After adding, continuing stirring 20min, centrifugal, washing, alcohol are washed, and are placed in vacuum drying oven the Cu-lyt. obtaining white in 70 DEG C of dry 10h.Product is tested through XRD, meets the standard diagram of the cuprous chloride crystal of JCPDS standard card 6-0344.
Embodiment 14
By 0.01molCu (NO3)2·3H2O and 0.02molNaOAc is dissolved in 50mL water, drips 0.04mol oxammonium hydrochloride. aqueous solution (5mL) under the stir speed (S.S.) of 25 DEG C and 1500-2000r/min, and time for adding controls at 5-10min;After adding, continuing stirring 20min, centrifugal, washing, alcohol are washed, and are placed in vacuum drying oven the Cu-lyt. obtaining white in 70 DEG C of dry 10h.Product is tested through XRD, meets the standard diagram of the cuprous chloride crystal of JCPDS standard card 6-0344.
Embodiment 15
By 0.01molCuSO4·5H2O and 0.01molNaOAc is dissolved in 5mL water, drips 0.005mol oxammonium hydrochloride. aqueous solution (2mL) under the stir speed (S.S.) of 25 DEG C and 1500-2000r/min, and time for adding controls at 1-5min;After adding, continuing stirring 20min, centrifugal, washing, alcohol are washed, and are placed in vacuum drying oven the Cu-lyt. obtaining white in 70 DEG C of dry 10h.Product is tested through XRD, meets the standard diagram of the cuprous chloride crystal of JCPDS standard card 6-0344.
Embodiment 16
By 0.01molCuSO4·5H2O and 0.01molNaOAc is dissolved in 20mL water, drips 0.03mol oxammonium hydrochloride. aqueous solution (5mL) under the stir speed (S.S.) of 25 DEG C and 1000-1500r/min, and time for adding controls at 5-10min;After adding, continuing stirring 20min, centrifugal, washing, alcohol are washed, and are placed in vacuum drying oven the Cu-lyt. obtaining white in 60 DEG C of dry 10h.Product is tested through XRD, meets the standard diagram of the cuprous chloride crystal of JCPDS standard card 6-0344.
Embodiment above describes the ultimate principle of the present invention, principal character and advantage; skilled person will appreciate that of the industry; the present invention is not restricted to the described embodiments; the principle that the present invention is simply described described in above-described embodiment and description; under the scope without departing from the principle of the invention; the present invention also has various changes and modifications, and these changes and improvements each fall within the scope of protection of the invention.