CN207891287U - A kind of catalyst mother liquor comprehensive recycling device in propenecarbonyl - Google Patents
A kind of catalyst mother liquor comprehensive recycling device in propenecarbonyl Download PDFInfo
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- CN207891287U CN207891287U CN201721788778.9U CN201721788778U CN207891287U CN 207891287 U CN207891287 U CN 207891287U CN 201721788778 U CN201721788778 U CN 201721788778U CN 207891287 U CN207891287 U CN 207891287U
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Abstract
The utility model is related to a kind of devices of the catalyst mother liquor comprehensive reutilization in propenecarbonyl；Including raw material heat exchanger, the first adsorption column, the second adsorption column, surge tank, de- butyraldehyde tower, butyraldehyde storage tank, de- high polymer tower, high polymer storage tank, reactor and centrifuge；First adsorption column is used for the absorption of rhodium in decaying catalyst mother liquor；Second adsorption column is used for the further absorption of rhodium in decaying catalyst mother liquor；De- butyraldehyde tower is used to mix the separation removal of butyraldehyde.De- high polymer tower is for trimer, the separation removal of unknown component.The reactor is used for the low temperature crystallization of triphenylphosphine.State separation of the centrifuge for triphenylphosphine after crystallizing.It solves the catalyst mother liquor in propenecarbonyl and a large amount of waste liquid is generated using burning pollution on the environment and extraction in noble metal removal process.It solves the loss to butyraldehyde and triphenylphosphine in the burning of catalyst mother liquor or nitrifying process, substantially increases the active principle utilization rate of catalyst mother liquor.
Description
Technical field
The utility model is directed to the catalyst mother liquor used in propenecarbonyl building-up process and carries out comprehensive reutilization, this reality
With the novel comprehensive reutilization especially for the rhodium used in commercial process/triphenyl phosphorus spent catalyst mother liquor
A kind of device.
Background technology
Octyl alconyl commercial plant is mainly using using oil-soluble rhodium/triphenyl phosphorus complex as the propylene of catalyst at present
Low pressure carbonylic synthesis technology, catalyst is often since the form of catalytic core rhodium in reaction process changes and loses catalytic activity
And the presence of impurity generates new complex compound in raw material, so that rhodium phosphine complex catalyst is lost catalytic activity, becomes dead catalyst
Mother liquor.Therefore often contain more impurity in the spent catalyst mother liquor generated during propenecarbonylization, as hydroformylation is anti-
It answers in spent rhodium catalyst solution containing there are many aldehydes, triphenyl phosphorus, higher olefins and high boiling organic polymers and other
The base-metal ion such as substances such as iron, nickel and inorganic chlorion, sulphion.Only recycle Noble Metal Rhodium, triphenyl in catalyst mother liquor
The useful organic matter such as phosphine, aldehydes cannot be effectively utilized, it will generate a large amount of waste.
The method for carrying out rhodium recycling for the catalyst that propenecarbonyl synthesis uses is mainly burning method, extraction and displacement
Method etc..CN201210436286.9 carries out processing using hydrogen peroxide to useless rhodium liquid makes the metal rhodium ion in the complex compound of rhodium send out
Raw redox reaction, the valence state of rhodium ion change, and ultimately form rhodium precipitation, and the remaining rhodium containing nearly 10% or so is molten
Concentrated processing obtains rhodium slag to liquid again, is burned in electric furnace, and carbon distribution remaining in lime-ash is removed to obtain containing other metals
The rhodium metal of impurity.CN201210437138.9 is existed as carrier using a certain amount of silica is added into spent rhodium catalyst
Destructive distillation roasting is carried out in high temperature furnace, the addition of silica reduces the loss in roasting process, the residue obtained middle dense salt of addition
Acid controls temperature, is passed through enough ozone, obtains unpurified chlorine rhodium acid solution.CN99106262.0 uses special burning process, right
Rhodium-containing catalyst waste liquid carries out burning ashing.CN201310483216.3 makes in solution rhodium with heavy using active metal as displacer
Shallow lake form is separated with rhodium catalyst waste liquid.CN201410505191.7 is in the concentration process of the useless rhodium liquid of low concentration, solving
The loss of rhodium and clustering round for rhodium is prevented in concentration process.
Current patent report is only to carry out a series of improvement to burning method, such as stringent temperature control carry out concentration and
The substances such as carrier silicas, sodium chloride are added in dead catalyst mother liquor reduces the loss of rhodium during the burning process, removal process
Middle organic compound combustion pollution on the environment is not improved.Active metal displacement method, extraction are on the surface not
Burned again, but in whole process a large amount of organic solvents use, will produce a large amount of dangerous waste solution can equally cause environment
Pollution, while can also cause the waste of resource.
Invention content
It is lost for rhodium under the low concentration used in propenecarbonyl building-up process the purpose of this utility model is to provide a kind of
The method and device of catalyst mother liquor comprehensive reutilization living, solves in previous decaying catalyst during the recycling of rhodium
There are the problem of and catalyst mother liquor in triphenylphosphine recycling.
The technical solution of the utility model is as follows：
A kind of catalyst mother liquor comprehensive recycling device in propenecarbonyl, including raw material heat exchanger, the first absorption
Column, the second adsorption column, surge tank, de- butyraldehyde tower, butyraldehyde storage tank, de- high polymer tower, high polymer storage tank, reactor and centrifuge；
It is characterized in that raw material heat exchanger is connected by raw material intake pipeline with feedstock transportation pump；First absorption column bottom feed inlet passes through
First absorption pipeline is connected with the material outlet of raw material heat exchanger；Second absorption column bottom feed inlet passes through the second absorption pipeline
It is connected with the first adsorption column top discharge mouth；Surge tank top feed mouth at the top of surge tank pipeline and the second adsorption column by going out
Material mouth is connected；The middle and lower part feed inlet of de- butyraldehyde tower passes through the bottom of the first separate pipeline and surge tank that are pumped equipped with surge tank
Discharge port is connected, and the de- butyraldehyde top of tower exports pipeline and butyraldehyde tank top import by being connected with butyraldehyde condenser
It is connected；De- high polymer tower middle and lower part feed inlet is by being connected with the bottom of the second separate pipeline and de- butyraldehyde tower of de- butyraldehyde tower pump
Portion's discharge port is connected, and the outlet of the de- high polymer top of tower is by being connected with the pipeline and high polymer of high polymer condenser
Tank top import is connected；Reactor feed mouth passes through the reactor line for being connected with triphenylphosphine mother liquor delivery pump and de- height
Polymers tower bottom discharge port is connected；Centrifuge feed inlet is connected by centrifuging pipeline with the discharge port of reactor, centrifuge
Discharge port exports for thick triphenylphosphine.
It is described as follows：
The raw material heat exchanger is used for the heating of raw material；The raw material heat exchanger passes through raw material intake pipeline and feedstock transportation
Pump is connected；
First adsorption column is used for the absorption of rhodium in dead catalyst mother liquor, the adsorbent of first adsorption column filling
It is sulfonation base silica column.The first absorption column bottom feed inlet is gone out by the raw material of the first absorption pipeline and raw material heat exchanger
Mouth is connected；
Second adsorption column is used for the further absorption of rhodium in dead catalyst mother liquor, ensures in decaying catalyst mother liquor
Rhodium is complete by absorption, and the adsorbent of second adsorption column filling is sulfonation base silica column.Second absorption column bottom
Feed inlet is connected by the second absorption pipeline with the first adsorption column top discharge mouth；
The surge tank top feed mouth is connected by surge tank pipeline with the second adsorption column top discharge mouth；
The de- butyraldehyde tower is used to mix the separation removal of butyraldehyde.The middle and lower part feed inlet of the de- butyraldehyde tower is by being equipped with
First separate pipeline of surge tank pump is connected with the bottom discharge mouth of surge tank, and the de- butyraldehyde top of tower outlet passes through connection
There is the pipeline of butyraldehyde condenser to be connected with butyraldehyde tank top import.
The de- high polymer tower is for trimer, the separation removal of unknown component.
The de- high polymer tower middle and lower part feed inlet passes through the second separate pipeline for being connected with de- butyraldehyde tower pump and de- butyraldehyde
The bottom discharge mouth of tower is connected, the outlet of the de- high polymer top of tower by be connected with the pipeline of high polymer condenser with
High polymer tank top import is connected.
The reactor is used for the low temperature crystallization of triphenylphosphine.The reactor feed mouth is by being connected with triphenylphosphine mother
The reactor line of liquid delivery pump is connected with de- high polymer tower bottom discharge port.
The separation of triphenylphosphine after the centrifuge is used to crystallize.The centrifuge feed inlet is by centrifuging pipeline and reacting
The discharge port of device is connected, and the centrifuge discharge port isolates thick triphenylphosphine.
The method for carrying out the catalyst mother liquor comprehensive reutilization in propenecarbonyl using the device of the invention；Using two
A adsorption column series connection, is as follows：
(1) dead catalyst mother liquor is sent into raw material heat exchanger first, is sent into after raw material heat exchanger is warming up to 65~85 DEG C
First adsorption column and the second adsorption column；First adsorption column and the second adsorption column bed are sulfonation base silica column；
(2) enter the dead catalyst mother liquor amount control of the first adsorption column and the second adsorption column adsorption bed 10~
50L/h；Dead catalyst mother liquor is 20~60min in the absorption resin bed residence time of the first adsorption column, in the second adsorption column
The absorption resin bed residence time be 30~60min；
(3) the dead catalyst mother liquor after the absorption of the second adsorption column enters the buffer tank, and buffered tank, which is sent into, takes off butyraldehyde tower
In；De- butyraldehyde tower is nitrogen subnormal ambient, by the control of de- butyraldehyde tower temperature degree at 75~95 DEG C, pressure control -0.1~-
0.07KPa；De- butyraldehyde column overhead mixing butyraldehyde steam enters after the condensation of butyraldehyde condenser in butyraldehyde storage tank；
(4) de- butyraldehyde tower bottom liquid is pumped into de- high polymer tower, it is nitrogen subnormal ambient to take off high polymer tower also, will be de- high poly-
For the control of object tower temperature degree at 140~240 DEG C, pressure control realizes the removal of trimer and unknown component in -0.1~-0.07KPa
With the concentration of triphenylphosphine；Overhead vapours enter high polymer storage tank through the condensation of high polymer condenser；
(5) the triphenylphosphine mother liquor after concentrating de- high polymer tower bottom of tower is pumped into the low temperature knot that reactor carries out triphenylphosphine
Partial crystallization goes out, and the temperature for controlling reactor is 0~-10 DEG C, after crystal is precipitated, is centrifuged through centrifuge, obtains thick triphenylphosphine；
(6) triphenylphosphine solid is first washed with water, is then dissolved with ethyl alcohol, evaporative crystallization recycles triphenylphosphine.
Above-mentioned dead catalyst mother liquor includes the catalyst mother liquor of inactivation and the catalyst mother liquor that activity reduces.
The function load capacity being grafted on above-mentioned silica column is 0.8-1mmol/g, sulfonation base silica column average grain diameter
200-500mm。
Rhodium in dead catalyst mother liquor is recycled, is included the following steps：
(1) by the sulfonation base silica column salt in the first adsorption column and the second adsorption column after absorption dead catalyst mother liquor
Acid carries out dissolution process, and by lysate condensing reflux, temperature is controlled at 85~90 DEG C, and fixed gas is handled by lye absorption；
(2) lysate is filtered, filter cake be sulfonation base silica column skeleton (silica), filtrate by sun from
Son absorption resin removes the foreign ions such as iron ion, nickel ion, the rhodium chloride solution purified；
(3) rhodium chloride solution after purification is concentrated under conditions of vacuum degree is -0.004~-0.01MPa
Evaporation, crystallization obtain rufous rhodium chloride crystal.
Rhodium in the dead catalyst mother liquor carries out the addition with sulfonation base silica column matter of hydrochloric acid in recycling step (1)
Amount is than being 4~6:1.
It realizes the catalyst mother liquor comprehensive recycling device in the propenecarbonyl of the utility model, is described in detail such as
Under：
Reached using the system and technology of the utility model and butyraldehyde and triphenylphosphine in dead catalyst mother liquor have been returned
It receives and the rhodium in dead catalyst mother liquor is recycled；It is described as follows：
1, butyraldehyde in dead catalyst mother liquor and triphenylphosphine are recycled, uses two adsorption column series connection, it is specific to walk
It is rapid as follows：
(1) dead catalyst mother liquor is pumped into raw material heat exchanger by feedstock transportation first, 65 is warming up to through raw material heat exchanger
The first adsorption column and the second adsorption column are sent into after~85 DEG C；First adsorption column and the second adsorption column bed are sulfonation Ji Guijiaoshu
Fat, for adsorbing the rhodium in dead catalyst mother liquor；For ensure catalyst mother liquor temperature it is identical as the temperature of adsorption bed or
It is close, the first adsorption column and the second adsorption column bed are warming up to 65~85 DEG C；
(2) enter the dead catalyst mother liquor amount control of the first adsorption column and the second adsorption column adsorption bed 10~
50L/h, and inlet amount needs to keep stablizing；Dead catalyst mother liquor is 20 in the absorption resin bed residence time of the first adsorption column
~60min is 30~60min in the absorption resin bed residence time of the second adsorption column；
(3) the dead catalyst mother liquor after the absorption of the second adsorption column enters the buffer tank, and buffered tank is pumped into de- butyraldehyde
In tower；De- butyraldehyde tower is nitrogen subnormal ambient, by the control of de- butyraldehyde tower temperature degree at 75~95 DEG C, pressure control -0.1~-
0.07KPa carries out low-temp low-pressure abjection mixing butyraldehyde；De- butyraldehyde column overhead mixing butyraldehyde steam condenses laggard through butyraldehyde condenser
Enter in butyraldehyde storage tank；
(4) de- butyraldehyde tower bottom liquid is pumped into de- high polymer tower, it is nitrogen subnormal ambient to take off high polymer tower also, will be de- high poly-
The control of object tower temperature degree at 140~240 DEG C, determine de- high polymer tower bottom materials in -0.1~-0.07KPa by pressure control
Phase sampling analysis, analyzes the triphenylphosphine of sample, the content of trimer, unknown component, realizes going for trimer and unknown component
Except the concentration with triphenylphosphine.Overhead vapours enter high polymer storage tank through the condensation of high polymer condenser, and main component is trimer
And unknown component；
(5) the triphenylphosphine mother liquor after concentrating de- high polymer tower bottom of tower is pumped into the low temperature knot that reactor carries out triphenylphosphine
Partial crystallization goes out, and the temperature for controlling reactor is 0~-10 DEG C, after crystal is precipitated, is centrifuged through centrifuge, obtains thick triphenylphosphine；
(6) triphenylphosphine solid is first washed with water, is then dissolved with ethyl alcohol, evaporative crystallization recycles triphenylphosphine；
2, the rhodium in dead catalyst mother liquor is recycled, is included the following steps：
(1) by the sulfonation base silica column salt in the first adsorption column and the second adsorption column after absorption dead catalyst mother liquor
Acid carries out dissolution process, and by lysate condensing reflux, temperature is controlled at 85~90 DEG C, and fixed gas is handled by lye absorption；
(2) lysate is filtered, filter cake be sulfonation base silica column skeleton (silica), filtrate by sun from
Son absorption resin removes the foreign ions such as iron ion, nickel ion, the rhodium chloride solution purified；
(3) rhodium chloride solution after purification is concentrated under conditions of vacuum degree is -0.004~-0.01MPa
Evaporation, crystallization obtain rufous rhodium chloride crystal.
It is had the following effects that using the utility model method：
1, it solves the catalyst mother liquor in propenecarbonyl to cause environment using burning in noble metal removal process
Pollution and extraction generate a large amount of waste liquid.
2, it solves the loss to butyraldehyde and triphenylphosphine in the burning of catalyst mother liquor or nitrifying process, substantially increases
The active principle utilization rate of catalyst mother liquor.
Description of the drawings
Attached drawing is the catalyst mother liquor comprehensive recycling device schematic diagram in the propenecarbonyl of the utility model
Specific implementation mode
The utility model is described in detail in the following with reference to the drawings and specific embodiments.
Catalyst mother liquor comprehensive recycling device in the propenecarbonyl of the utility model as shown in drawings, including
Raw material heat exchanger 2, the first adsorption column 3, the second adsorption column 4, surge tank 5, de- butyraldehyde tower 7, butyraldehyde storage tank 10, de- high polymer tower
13, high polymer storage tank 12, reactor 15 and centrifuge 16；It is characterized in that raw material heat exchanger 2 passes through raw material intake pipeline and raw material
Delivery pump 1 is connected；The material outlet phase that first adsorption column, 3 bottom feed inlet passes through the first absorption pipeline and raw material heat exchanger 2
Connection；Second adsorption column, 4 bottom feed inlet is connected by the second absorption pipeline with 3 top discharge mouth of the first adsorption column；Buffering
5 top feed mouth of tank is connected by surge tank pipeline with 4 top discharge mouth of the second adsorption column；The middle and lower part of de- butyraldehyde tower 7 into
Material mouth is connected by the first separate pipeline equipped with surge tank pump 6 with the bottom discharge mouth of surge tank 5, the de- butyraldehyde tower 7
Top exit is connected by being connected with the pipeline of butyraldehyde condenser 8 with 10 top inlet of butyraldehyde storage tank；In de- high polymer tower 13
Lower part feed inlet is connected by being connected with the second separate pipeline of de- butyraldehyde tower pump 9 with the bottom discharge mouth of de- butyraldehyde tower 7, institute
De- 13 top exit of high polymer tower stated is by being connected with the pipeline of high polymer condenser 11 and 12 top inlet of high polymer storage tank
It is connected；15 feed inlet of reactor is by being connected with the reactor line of triphenylphosphine mother liquor delivery pump 14 and de- high polymer tower 13
Bottom discharge mouth is connected；16 feed inlet of centrifuge is connected by centrifuging pipeline with the discharge port of reactor 15, centrifuge 16
Discharge port exports for thick triphenylphosphine.
1, butyraldehyde in dead catalyst mother liquor and triphenylphosphine are recycled, uses two adsorption column series connection, it is specific to walk
It is rapid as follows：
(1) dead catalyst mother liquor is pumped into raw material heat exchanger 2 by feedstock transportation pump 1 first, is warming up to through raw material heat exchanger 2
The first adsorption column 3 and the second adsorption column 4 are sent into after 65~85 DEG C；First adsorption column 3 and 4 bed of the second adsorption column are sulfonation base
Silica column, for adsorbing the rhodium in dead catalyst mother liquor；For the temperature phase of the temperature and adsorption bed of guarantee catalyst mother liquor
It is same or close, the first adsorption column 3 and the second adsorption column bed 4 are warming up to 65~85 DEG C；
(2) enter the dead catalyst mother liquor amount control of 4 adsorption bed of the first adsorption column 3 and the second adsorption column 10~
50L/h, and inlet amount needs to keep stablizing.Dead catalyst mother liquor is in the absorption resin bed residence time of the first adsorption column 3
20~60min is 30~60min in the absorption resin bed residence time of the second adsorption column 4.
(3) the dead catalyst mother liquor after the absorption of the second adsorption column 4 enters in surge tank 5, and buffered tank pump 6 is pumped into de- fourth
In aldehyde tower 7.De- butyraldehyde tower 7 is nitrogen subnormal ambient, and by the control of de- 7 temperature of butyraldehyde tower at 75~95 DEG C, pressure is controlled -0.1
~-0.07KPa carries out low-temp low-pressure abjection mixing butyraldehyde.De- butyraldehyde 7 tower top mixing butyraldehyde steams of tower are cold through butyraldehyde condenser 8
Enter in butyraldehyde storage tank 10 after solidifying.
(4) 7 bottom liquid pump of de- butyraldehyde tower is entered in de- high polymer tower 13, it is nitrogen subnormal ambient to take off high polymer tower 13 also, will
The 13 temperature control of de- high polymer tower is at 140~240 DEG C, and pressure control is in -0.1~-0.07KPa, to taking off 13 bottom of tower of high polymer tower
Substance carries out regular sampling analysis, analyzes the triphenylphosphine of sample, the content of trimer, unknown component, realizes trimer and not
The removal of main constituent and the concentration of triphenylphosphine.Top steam enters high polymer storage tank 12 via the condensation of high polymer condenser 11,
Main component is trimer and unknown component.
(5) the triphenylphosphine mother liquor after concentrating de- 13 bottom of tower of high polymer tower is pumped into reactor 15 and carries out the low of triphenylphosphine
Temperature crystallization is precipitated, and the temperature of control reactor 15 is 0~-10 DEG C, after crystal is precipitated, is centrifuged through centrifuge 16, obtains thick triphen
Base phosphine.
(6) triphenylphosphine solid is first washed with water, is then dissolved with ethyl alcohol, evaporative crystallization recycles triphenylphosphine.
Above-mentioned dead catalyst mother liquor includes the catalyst mother liquor of inactivation and the catalyst mother liquor that activity reduces.
The function load capacity being grafted on above-mentioned silica column is 0.8-1mmol/g, sulfonation base silica column average grain diameter
200-500mm。
2, the rhodium in dead catalyst mother liquor is recycled, is included the following steps：
(1) by the sulfonation base silica column salt in the first adsorption column and the second adsorption column after absorption dead catalyst mother liquor
Acid carries out dissolution process, and by lysate condensing reflux, temperature is controlled at 85~90 DEG C, and fixed gas is handled by lye absorption；
(2) lysate is filtered, filter cake be sulfonation base silica column skeleton (silica), filtrate by sun from
Son absorption resin removes the foreign ions such as iron ion, nickel ion, the rhodium chloride solution purified；
(3) rhodium chloride solution after purification is concentrated under conditions of vacuum degree is -0.004~-0.01MPa
Evaporation, crystallization obtain rufous rhodium chloride crystal.
Wherein the addition of hydrochloric acid and sulfonation base silica column mass ratio are 4~6:1.
Embodiment 1
1, in dead catalyst mother liquor butyraldehyde and triphenylphosphine recycle, use the series connection of two adsorption columns, specifically
Include the following steps：
(1) the dead catalyst mother liquor of inactivation is pumped into raw material heat exchanger 2 by feedstock transportation pump 1 first, through raw material heat exchanger 2
The first adsorption column 3 and the second adsorption column 4 are sent into after being warming up to 65 DEG C；First adsorption column 3 and 4 bed of the second adsorption column are sulfonation
Base silica column, (the function load capacity being grafted on silica column is 0.8mmol/g, sulfonation base silica column average grain diameter 200-
500mm) it is used to adsorb the rhodium in dead catalyst mother liquor；For ensure catalyst mother liquor temperature it is identical as the temperature of adsorption bed or
Person is close, and the first adsorption column 3 and the second adsorption column bed 4 are warming up to 65 DEG C；
(2) the dead catalyst mother liquor amount for entering 4 adsorption bed of the first adsorption column 3 and the second adsorption column is controlled in 10L/
H, and inlet amount needs to keep stablizing.Dead catalyst mother liquor is in the absorption resin bed residence time of the first adsorption column 3
20min is 30min in the absorption resin bed residence time of the second adsorption column 4.
(3) the dead catalyst mother liquor after the absorption of the second adsorption column 4 enters in surge tank 5, and buffered tank pump 6 is pumped into de- fourth
In aldehyde tower 7.De- butyraldehyde tower 7 is nitrogen subnormal ambient, and by the control of de- 7 temperature of butyraldehyde tower at 75 DEG C, pressure is controlled in -0.1KPa,
Carry out low-temp low-pressure abjection mixing butyraldehyde.De- 7 tower top mixing butyraldehyde steam of butyraldehyde tower enters butyraldehyde after the condensation of butyraldehyde condenser 8
In storage tank 10.
(4) 7 bottom liquid pump of de- butyraldehyde tower is entered in de- high polymer tower 13, it is nitrogen subnormal ambient to take off high polymer tower 13 also, will
The 13 temperature control of de- high polymer tower is at 140 DEG C, and pressure control is in -0.1KPa, after evaporating 2h, to taking off 13 bottom materials of high polymer tower
It is sampled analysis, the content of wherein triphenylphosphine reaches 40%.
(5) the triphenylphosphine mother liquor after concentrating de- 13 bottom of tower of high polymer tower is pumped into reactor 15 and carries out the low of triphenylphosphine
Temperature crystallization is precipitated, and the temperature of control reactor 15 is 0 DEG C, after crystal is precipitated, is centrifuged through centrifuge 16, obtains thick triphenylphosphine.
(6) triphenylphosphine solid is first washed with water, is then dissolved with ethyl alcohol, evaporative crystallization recycles triphenylphosphine.
2, the rhodium in dead catalyst mother liquor is recycled：Specifically include following steps：
(1) by the sulfonation base silica column salt in the first adsorption column and the second adsorption column after absorption dead catalyst mother liquor
Acid carries out dissolution process, and the addition of hydrochloric acid is 4 with the mass ratio of sulfonation base silica column:1, by lysate condensing reflux, temperature
At 85 DEG C, fixed gas is handled by lye absorption for degree control；
(2) lysate is filtered, filter cake be sulfonation base silica column skeleton (silica), filtrate by sun from
Son absorption resin removes the foreign ions such as iron ion, nickel ion, the rhodium chloride solution purified, wherein rhodium chloride solution
In iron content be 2ppm, nickel content is not detected；
(3) by rhodium chloride solution after purification under conditions of vacuum degree is -0.004MPa, concentration and evaporation, knot are carried out
Crystalline substance obtains rufous rhodium chloride crystal.
Embodiment 2
1, in dead catalyst mother liquor butyraldehyde and triphenylphosphine recycle, use the series connection of two adsorption columns, specifically
Include the following steps：
(1) the dead catalyst mother liquor that activity reduces is pumped into raw material heat exchanger 2 by feedstock transportation pump 1 first, is changed through raw material
Hot device 2 is sent into the first adsorption column 3 and the second adsorption column 4 after being warming up to 75 DEG C；First adsorption column 3 and 4 bed of the second adsorption column are equal
For sulfonation base silica column, (the function load capacity being grafted on silica column is 0.9mmol/g, sulfonation base silica column average grain diameter
200-500mm), for adsorbing the rhodium in dead catalyst mother liquor；For the temperature of the temperature and adsorption bed of guarantee catalyst mother liquor
It is same or similar, the first adsorption column 3 and the second adsorption column bed 4 are warming up to 75 DEG C；
(2) the dead catalyst mother liquor amount for entering 4 adsorption bed of the first adsorption column 3 and the second adsorption column is controlled in 30L/
H, and inlet amount needs to keep stablizing.Dead catalyst mother liquor is in the absorption resin bed residence time of the first adsorption column 3
40min is 45min in the absorption resin bed residence time of the second adsorption column 4.
(3) the dead catalyst mother liquor after the absorption of the second adsorption column 4 enters in surge tank 5, and buffered tank pump 6 is pumped into de- fourth
In aldehyde tower 7.De- butyraldehyde tower 7 is nitrogen subnormal ambient, and by the control of de- 7 temperature of butyraldehyde tower at 85 DEG C, pressure is controlled in -0.08KPa,
Carry out low-temp low-pressure abjection mixing butyraldehyde.De- 7 tower top mixing butyraldehyde steam of butyraldehyde tower enters fourth after being condensed via butyraldehyde condenser 8
In aldehyde storage tank 10.
(4) 7 bottom liquid pump of de- butyraldehyde tower is entered in de- high polymer tower 13, it is nitrogen subnormal ambient to take off high polymer tower 13 also, will
The 13 temperature control of de- high polymer tower is at 190 DEG C, and pressure control is in -0.08KPa, after evaporating 2h, to taking off 13 bottoms of high polymer tower
Matter is sampled analysis, and the content of wherein triphenylphosphine reaches 60%.
(5) the triphenylphosphine mother liquor after concentrating de- 13 bottom of high polymer tower is pumped into reactor 15 and carries out the low of triphenylphosphine
Temperature crystallization is precipitated, and the temperature of control reactor 15 is -5 DEG C, after crystal is precipitated, is centrifuged through centrifuge 16, obtains thick triphenylphosphine.
(6) triphenylphosphine solid is first washed with water, is then dissolved with ethyl alcohol, evaporative crystallization recycles triphenylphosphine.
2, the rhodium in dead catalyst mother liquor is recycled, is included the following steps：
(1) by the sulfonation base silica column salt in the first adsorption column and the second adsorption column after absorption dead catalyst mother liquor
Acid carries out dissolution process, and the addition of hydrochloric acid is 5 with the mass ratio of sulfonation base silica column:1, by lysate condensing reflux, temperature
At 87 DEG C, fixed gas is handled by lye absorption for degree control；
(2) lysate is filtered, filter cake be sulfonation base silica column skeleton (silica), filtrate by sun from
The foreign ions such as son absorption resin removing iron ion, nickel ion, the rhodium chloride solution purified, after testing, rhodium chloride
Iron content in solution is 1ppm, nickel content 1ppm；
(3) by rhodium chloride solution after purification under conditions of vacuum degree is -0.006MPa, concentration and evaporation, knot are carried out
Crystalline substance obtains rufous rhodium chloride crystal.
Embodiment 3
1, first in dead catalyst mother liquor butyraldehyde and triphenylphosphine recycle, use the series connection of two adsorption columns,
Specifically include following steps：
(1) the dead catalyst mother liquor of inactivation is pumped into raw material heat exchanger 2 by feedstock transportation pump 1 first, through raw material heat exchanger 2
The first adsorption column 3 and the second adsorption column 4 are sent into after being warming up to 85 DEG C；First adsorption column 3 and 4 bed of the second adsorption column are sulfonation
(the function load capacity being grafted on silica column is 1mmol/g, sulfonation base silica column average grain diameter 200- to base silica column
500mm), for adsorbing the rhodium in dead catalyst mother liquor；Temperature to ensure catalyst mother liquor is identical as the temperature of adsorption bed
Or it is close, the first adsorption column 3 and the second adsorption column bed 4 are warming up to 85 DEG C；
(2) the dead catalyst mother liquor amount for entering 4 adsorption bed of the first adsorption column 3 and the second adsorption column is controlled in 50L/
H, and inlet amount needs to keep stablizing.Dead catalyst mother liquor is in the absorption resin bed residence time of the first adsorption column 3
60min is 60min in the absorption resin bed residence time of the second adsorption column 4.
(3) the dead catalyst mother liquor after the absorption of the second adsorption column 4 enters in surge tank 5, and buffered tank pump 6 is pumped into de- fourth
In aldehyde tower 7.De- butyraldehyde tower 7 is nitrogen subnormal ambient, and by the control of de- 7 temperature of butyraldehyde tower at 95 DEG C, pressure is controlled in -0.07KPa,
Carry out low-temp low-pressure abjection mixing butyraldehyde.7 kettle top mixing butyraldehyde steam of de- butyraldehyde tower enters butyraldehyde after the condensation of butyraldehyde condenser 8
In storage tank 10.
(4) 7 bottom liquid pump of de- butyraldehyde tower is entered in de- high polymer tower 13, it is nitrogen subnormal ambient to take off high polymer tower 13 also, will
The 13 temperature control of de- high polymer tower is at 240 DEG C, and pressure control is in -0.07KPa, after evaporating 2h, to taking off 13 bottoms of high polymer tower
The content of matter sampling analysis, wherein triphenylphosphine reaches 75%.
(5) the triphenylphosphine mother liquor after concentrating de- 13 bottom of high polymer tower is pumped into reactor 15 and carries out the low of triphenylphosphine
Temperature crystallization is precipitated, and the temperature of control reactor 15 is -10 DEG C, after crystal is precipitated, is centrifuged via centrifuge 16, obtains thick triphenyl
Phosphine.
(6) triphenylphosphine solid is first washed with water, is then dissolved with ethyl alcohol, evaporative crystallization recycles triphenylphosphine.
2, the rhodium in dead catalyst mother liquor is recycled, is included the following steps：
(1) by the sulfonation base silica column salt in the first adsorption column and the second adsorption column after absorption dead catalyst mother liquor
Acid carries out dissolution process, and the addition of hydrochloric acid is 6 with the mass ratio of sulfonation base silica column:1, by lysate condensing reflux, temperature
At 90 DEG C, fixed gas is handled by lye absorption for degree control；
(2) lysate is filtered, filter cake be sulfonation base silica column skeleton (silica), filtrate by sun from
Son absorption resin removes the foreign ions such as iron ion, nickel ion, the rhodium chloride solution purified, wherein rhodium chloride solution
In iron content be not detected, nickel content is not detected；
(3) by rhodium chloride solution after purification under conditions of vacuum degree is -0.01MPa, concentration and evaporation, crystallization are carried out
Obtain rufous rhodium chloride crystal.
Claims (1)
1. the catalyst mother liquor comprehensive recycling device in a kind of propenecarbonyl, including raw material heat exchanger, the first adsorption column,
Second adsorption column, surge tank, de- butyraldehyde tower, butyraldehyde storage tank, de- high polymer tower, high polymer storage tank, reactor and centrifuge；It is special
Sign is that raw material heat exchanger is connected by raw material intake pipeline with feedstock transportation pump；First absorption column bottom feed inlet passes through first
Absorption pipeline is connected with the material outlet of raw material heat exchanger；Second absorption column bottom feed inlet passes through the second absorption pipeline and the
One adsorption column top discharge mouth is connected；Surge tank top feed mouth passes through surge tank pipeline and the second adsorption column top discharge mouth
It is connected；The middle and lower part feed inlet of de- butyraldehyde tower passes through the bottom discharge of the first separate pipeline and surge tank that are pumped equipped with surge tank
Mouth is connected, and the de- butyraldehyde top of tower outlet is connected by being connected with the pipeline of butyraldehyde condenser with butyraldehyde tank top import
It is logical；De- high polymer tower middle and lower part feed inlet is gone out by the second separate pipeline and the bottom of de- butyraldehyde tower for being connected with de- butyraldehyde tower pump
Material mouth is connected, and the outlet of the de- high polymer top of tower is by being connected with the pipeline and high polymer storage tank of high polymer condenser
Top inlet is connected；Reactor feed mouth passes through the reactor line for being connected with triphenylphosphine mother liquor delivery pump and de- high polymer
Tower bottom discharge port is connected；Centrifuge feed inlet is connected by centrifuging pipeline with the discharge port of reactor, centrifuge discharging
Mouth is that thick triphenylphosphine exports.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201721788778.9U CN207891287U (en) | 2017-12-19 | 2017-12-19 | A kind of catalyst mother liquor comprehensive recycling device in propenecarbonyl |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201721788778.9U CN207891287U (en) | 2017-12-19 | 2017-12-19 | A kind of catalyst mother liquor comprehensive recycling device in propenecarbonyl |
Publications (1)
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| Country | Link |
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