CN109678660A - A kind of improvement technique producing 1,4-butanediol - Google Patents

A kind of improvement technique producing 1,4-butanediol Download PDF

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Publication number
CN109678660A
CN109678660A CN201910115957.3A CN201910115957A CN109678660A CN 109678660 A CN109678660 A CN 109678660A CN 201910115957 A CN201910115957 A CN 201910115957A CN 109678660 A CN109678660 A CN 109678660A
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China
Prior art keywords
acetylene
formaldehyde
nitrae
isosorbide
butynediols
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Inventor
边利利
屈战成
张进华
樊小明
段贝贝
翟琛
郭婷
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Shaanxi Shan Hua Coal Chemical Industry Group Co ltd
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Shaanxi Shan Hua Coal Chemical Industry Group Co ltd
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Priority to CN201910115957.3A priority Critical patent/CN109678660A/en
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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
    • C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
    • C07C29/172—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds with the obtention of a fully saturated alcohol
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/613—10-100 m2/g
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/633—Pore volume less than 0.5 ml/g
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/635—0.5-1.0 ml/g
    • 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
    • C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
    • C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
    • C07C29/42—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones with compounds containing triple carbon-to-carbon bonds, e.g. with metal-alkynes

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The present invention provides a kind of improvement technique for producing 1,4-butanediol, acetylene and formaldehyde is first used to prepare Isosorbide-5-Nitrae-butynediols for raw material, then Isosorbide-5-Nitrae-butynediols high-pressure hydrogenation is converted into 1,4-butanediol, the pH value > 3.0 of formaldehyde.Since previous formaldehyde pH value maintains essentially between 2.5-2.6, the pH value of formaldehyde is increased to 3.0 or more, the day production capacity of BDO is made from 240t to be increased to 350t by the present invention by increasing liquid alkaline flusher at the top of formaldehyde absorbing tower.

Description

A kind of improvement technique producing 1,4-butanediol
Technical field
The present invention relates to BDO production field more particularly to a kind of improvement techniques for producing 1,4-butanediol.
Background technique
1,4-butanediol (BDO) is colourless oil liquid, water-miscible, and is dissolved in methanol, ethyl alcohol, acetone, slightly soluble In ether.In the U.S. and West Europe, more than half 1,4-butanediol (BDO) is for producing tetrahydrofuran, secondly for production γ- Butyrolactone and polybutylene terephthalate (PBT) (polybutylene terephthalate (PBT) is the engineering plastics in rapidly developing).1,4- Butanediol is as cahin extension agent and polyester raw material for producing polyurethane elastomer and flexible polyurethane foam；1,4- butanediol Esters obtained are the good plasticizer of cellulose, polyvinyl chloride, polyacrylate and polyesters.In addition, due to Isosorbide-5-Nitrae-fourth Glycol has good hygroscopicity and increases flexibility, can make gelatin softening agent and water absorbing agent, the processing of glassine paper and other unused paper Agent can also prepare N-Methyl pyrrolidone, n-vinyl pyrrolidone and other pyrrolidinone derivatives etc..
Although the technique of production 1,4- butanediol (BDO) has: (1) using formaldehyde and acetylene as Reppe method (the alkynes aldehyde of raw material Method)；(2) using butadiene and acetic acid as the butadiene acetoxylation method of raw material；(3) using propylene oxide/propenyl as raw material Propylene oxide method；(4) using normal butane/cis-butenedioic anhydride as the Davy method of raw material.Since domestic butadiene and propylene oxide are more short, adopt It is not yet mature with both technologies production 1,4-butanediol (BDO), production technology is selected according to resources advantage, is led at home If Reppe method (acetylene-formaldehyde process).So-called Reppe method, be first with acetylene and formaldehyde in the presence of acetylene copper catalyst, 92kPa, 1,4- butynediols (BYD) is made under the conditions of 80-95 DEG C；Isosorbide-5-Nitrae-butynediols (BYD) high-pressure hydrogenation is converted into 1,4-butanediol, Sterling is obtained through distilation again.
During actual production 1,4-butanediol (BDO), is influenced by BDO device, be not able to achieve long period always Stable operation, production capacity also fail always to reach design production capacity.
Summary of the invention
Production capacity low defect when in order to overcome production 1,4-butanediol (BDO), the present invention provides a kind of production Isosorbide-5-Nitrae-fourths The improvement technique of glycol improves BDO production capacity by adjusting the pH value of formaldehyde products.
Realize that the technical solution of the object of the invention is as follows:
A kind of improvement technique producing 1,4-butanediol first uses acetylene and formaldehyde to prepare Isosorbide-5-Nitrae-butynediols for raw material, then will Isosorbide-5-Nitrae-butynediols high-pressure hydrogenation is converted into 1,4-butanediol, the pH value > 3.0 of formaldehyde.Since previous formaldehyde pH value is tieed up substantially It holds between 2.5-2.6, the present invention is improved the pH value of formaldehyde by increasing liquid alkaline flusher at the top of formaldehyde absorbing tower To 3.0 or more, the day production capacity of BDO is made from 240t to be increased to 350t.
It as a further improvement of the present invention, further include acetylene acid pickling step, the second before the acetylene is reacted with formaldehyde Concentration >=85% of acid solution when acetylenic acid is washed.The concentration of acid solution is increased to 85% or more from 75%(wt%) by the present invention, makes acetylene The acetylene that generator generates purity after pickling is higher (removing the impurity such as hydrogen sulfide and hydrogen phosphide), with the second of condition homogenous quantities part Alkynes, formaldehyde prepare the more efficient of 1,4- butynediols (BYD).
As a further improvement of the present invention, the concentration of the acid solution is 89% ~ 93%.The present invention using concentration be 89% ~ 93% acid solution pickling acetylene, acetylene and Isosorbide-5-Nitrae-butynediols prepared by formaldehyde are more efficient.
As a further improvement of the present invention, the acetylene is occurred using more acetylene generator preparations in every acetylene It is respectively provided with the displacement pipeline being connected to ambient systems on device, realizes that separate unit generator cuts out system and individually overhauls.Because of ethynylation Catalyst only has 2-3 months service life, causes to need the replacement ethynylation catalyst that frequently stops production when BDO production system, cause Whole system operation continuity is poor, has more acetylene generators in system of the invention, is arranged on every acetylene generator One displacement pipeline realizes that separate unit generator cuts out system and individually overhauls.When a certain acetylene generator needs to overhaul, pass through Acetylene generator is individually cut out the maintenance of BDO production system by displacement pipeline, does not influence the continuous operation of BDO production system.
As a further improvement of the present invention, the formaldehyde and acetylene prepare Isosorbide-5-Nitrae-butine two in ethynylation device The operating pressure of alcohol, the ethynylation device is greater than 100 kpa.In common process, the pressure of ethynylation device is lower than 100 Kpa, the preferably kpa of 92 kpa ~ 98, the present invention are anti-ethynylation under the premise of formaldehyde pH value increases, acid solutions increase It answers the pressure in device to be turned up to 100 kpa or more, substantially increases production efficiency, improve production capacity.Technique is in reality after improvement After being applied in production, in terms of the operating condition of nearly two batches ethynylation catalyst, the runing time of single batch ethynylation catalyst with BDO yield is significantly improved.
As a further improvement of the present invention, serpentine coil, stream in the serpentine coil are equipped with inside the ethynylation device The dynamic high-temp liquid having for heating ethynylation device inner cavity.Heat exchange of the present invention by high-temp liquid, ethynylation device inner cavity Temperature control at 100 DEG C ~ 150 DEG C, operating pressure be greater than 100 kpa under the premise of control ethynylation device inner cavity temperature, Improve production capacity.
As a further improvement of the present invention, it is added during the Isosorbide-5-Nitrae-butynediols is converted into 1,4-butanediol Hydrogenation catalyst, the specific surface area of the hydrogenation catalyst are 60~130m20.35~0.6ml/g of/g, Kong Rongwei.High-pressure hydrogenation The core point of step is catalyst, which requires catalyst to have higher hydrogenation activity, selectivity, wherein noble metal one Divide and introduced in a manner of dipping, another part introducing when preparing carrier, (hydrogenation catalyst is effective with conventional Nickel Aluminium Alloy Powder Ingredient is nickel) it compares, the catalyst surface area and Kong Rongjun that the present invention selects are larger, excellent catalytic effect.
Specific embodiment
Below with reference to each embodiment, the present invention is described in detail, but it should be stated that, these embodiments are simultaneously Non- limitation of the present invention, those of ordinary skill in the art are according to these embodiments in made function, method or structure Equivalent transformation or substitution, all belong to the scope of protection of the present invention within.
Embodiment 1:
BDO is a kind of important fine chemical product, mainly for the production of tetrahydrofuran (THF), gamma-butyrolacton (GBL), is gathered Mutual-phenenyl two acid bromide two alcohol ester (PBT), polyurethane (PU), copolyester ether (COPEs), poly- tetramethylene glycol ether, N- methyl Pyrrolidones (NMP), polyvinylpyrrolidone (PVP) etc..By taking PBT as an example, in recent years, PBT is mainly used for PBT modification, PBT The fields such as wire drawing, PBT membrane, optical fiber jacket modified can be widely applied to automobile manufacture, electric, instrument instrument enhancing The fields such as table, lighting apparatus, household electrical appliances weaving, mechanical and communication, in addition, being also used to synthesize vitamin B6, pesticide, herbicide and molten Agent, humidizer, plasticizer, medicine intermediate, chain extender and adhesive etc..
It is industrial at present use using formaldehyde and acetylene as the Reppe method technique of raw material in numerous BDO production technologies A most technology paths.Be carried out in two steps by the technical process of Reppe method production BDO: the first step is that formaldehyde and acetylene exist Acetylene copper catalyst effect is lower to generate BYD；Second step is that BYD catalytic hydrogenation generates BDO.
The method that 1,4- butynediols (BYD) catalytic hydrogenation mainly uses two-stage hydrogenation at present.One-stage hydrogenation is stirred using band The slurry bed reactor mixed, catalyst are Raney's nickel, 50-60 DEG C of reaction temperature, reaction pressure 1.5-3.0Mpa(G), one section plus Material after hydrogen is segregated into secondary hydrogenation through catalyst, and one-stage hydrogenation reaction can be such that Isosorbide-5-Nitrae-butynediols conversion ratio reaches 90-95%.Secondary hydrogenation use fixed bed high-pressure hydrogenation reactor, nickel catalyst, 110-165 DEG C of reaction temperature, reaction pressure 7-30Mpa(G).Therefore, the main task of secondary hydrogenation is that the Isosorbide-5-Nitrae-butynediols that will be converted continues to be hydrogenated to 1.4- Butanediol.
Industrial existing hydrogenation catalyst filling is mixed packing method, and it is inclined to will cause bottom dealuminzation in activation process Height, in addition activation caused by size particles load in mixture is uneven, the bottom higher little particle of activity is more vulnerable to the shadow of copper bismuth ion It rings, comprehensive various factors, industrial BDO device more catalyst changeout is more frequent at present, short only 2-3 months, replaces every time Catalyst occupies a large amount of production time, has seriously affected factory economy benefit and product quality.
A kind of improvement technique for producing 1,4-butanediol, first uses acetylene and formaldehyde for raw material system disclosed in the present embodiment Standby Isosorbide-5-Nitrae-butynediols, then Isosorbide-5-Nitrae-butynediols high-pressure hydrogenation is converted into 1,4-butanediol, the pH value > 3.0 of formaldehyde.Due to Previous formaldehyde pH value maintains essentially between 2.5-2.6, and the present embodiment is sprayed by increasing liquid alkaline at the top of formaldehyde absorbing tower Device is spilt, the pH value of formaldehyde is increased to 3.0 or more, the day production capacity of BDO is made from 240t to be increased to 350t.
Acetylene further includes acetylene acid pickling step before reacting with formaldehyde, concentration >=85% of acid solution when the acetylene pickling.This The concentration of acid solution is increased to 85% or more from 75%(wt%) by embodiment, and the acetylene for generating acetylene generator is pure after pickling Du Genggao (removes the impurity such as hydrogen sulfide and hydrogen phosphide), and acetylene, the formaldehyde with condition homogenous quantities part prepare Isosorbide-5-Nitrae-butynediols (BYD) more efficient.
The concentration of acid solution is 89% ~ 93%.The acid solution pickling acetylene that the present embodiment is 89% ~ 93% using concentration, acetylene It is more efficient with the 1,4- butynediols of formaldehyde preparation.
For the present embodiment by changing operating parameter, dense acetylene purification pickling tower original design operation operation acid is 75%(wt.), And it this time improves and acid dense is mainly increased to 85% or more (preferably 85%)；Ethynylation pressure origin operation pressure 92kpa, now changes Operating pressure 103kpa, the pressure of ethynylation device are adjusted by included pressure regulator.
Before the hydrogenation catalyst for not improving the present embodiment, original hydrogenation catalyst effective component is nickel, traditional Hydrogenation catalyst is Nickel Aluminium Alloy Powder (being commonly called as Raney's nickel catalyst), is the unformed powder of silver gray before Raney's nickel catalyst activation (Nickel Aluminium Alloy Powder) has moderate combustibility, has in the presence of water partial activation and generates hydrogen and easily agglomerates, long It is exposed to easy-weathering in air long.It is greyish black coloured particles after Nickel Aluminium Alloy Powder activation, has active hydrogen, it is extremely unstable.To understand The unstable problem of certainly existing hydrogenation catalyst, the present embodiment select surface area and the biggish catalyst of Kong Rongjun.High pressure adds The core point of hydrogen step is catalyst, which requires catalyst to have higher hydrogenation activity, selectivity, wherein noble metal one Part is introduced in a manner of impregnating, another part introducing when preparing carrier, and (hydrogenation catalyst has with conventional Nickel Aluminium Alloy Powder Effect ingredient is nickel) it compares, the catalyst surface area and Kong Rongjun that the present embodiment is selected are larger, excellent catalytic effect.The present embodiment exists Isosorbide-5-Nitrae-butynediols is converted into that hydrogenation catalyst is added during 1,4-butanediol, and the specific surface area of hydrogenation catalyst is 60~ 130m20.35~0.6ml/g of/g, Kong Rongwei.The core point of high-pressure hydrogenation step is catalyst, the step require catalyst have compared with High hydrogenation activity, selectivity, wherein noble metal a part is introduced in a manner of impregnating, and another part draws when preparing carrier Enter, compared with conventional Nickel Aluminium Alloy Powder (hydrogenation catalyst effective component is nickel), the catalyst surface area of the present embodiment selection It is larger with Kong Rongjun, excellent catalytic effect.
Due to the change of hydrogenation catalyst, former filler material is also changed to resistance to high-intensitive corrosion and rubbed new by the present embodiment Profile matter, filler combination mode are also optimized.Hydrogenation catalyst is divided into two groups by the present embodiment, and one group is that specific surface area is 60 ~ 100 hydrogenation catalyst, another group is hydrogenation catalyst that specific surface area is 101 ~ 130, first group of hydrogenation catalyst and the Two groups of hydrogenation catalysts are arranged in ethynylation device inner laminated, and the lower end and upper end of ethynylation device are respectively set first group and add Hydrogen catalyst, second group of hydrogenation catalyst are placed on the centre of ethynylation device.Two groups of hydrogenation catalysts are by mixing What hydrogenation catalyst was sieved.Since the diameter of big specification is big, the diameter of small dimension is small, after overactivation, although small Specification hydrogenation catalyst picking it is more can lose it is amount of activated, but the hydrogenation catalyst of small dimension activity still relatively It is high.The purpose that the filler of the present embodiment is arranged in this way is in activation process, and first group of hydrogenation catalyst will not excessively be lived Change, to substantially increase hydrogenation activity, and catalyst life can be improved.
The present embodiment gives influence BDO device capbility reason and determines table, and the table is as follows:
Serial number Reason
1 Product formaldehyde PH is relatively low
2 Formaldehyde fan trouble is more, influences system loading
3 Acetylene generator cannot individually cut out system overhaul
4 Acetylene pulp water effect of settling is poor
5 Acetylene purifying device technique is slightly different with design
6 Ethynylation device pressure is relatively low compared with design
7 One phase ethynylation device technique fluctuation of service
8 Hydrogenation catalyst operating status is bad
9 Vacuum pump set operating status is poor
10 P8201 operating status is poor
11 System liquid waste processing pressure is big
12 System wastewater treatment pressure is big
BDO yield, ethynylation catalyst statistical form after improvement；
It chemically reacts for angle, the output of BDO by the purity of acetylene and formaldehyde, reaction environment (PH, temperature, pressure) and is urged Agent efficiency determines, counts from the yield data of comparison, and the lower equipment that mainly should be of production capacity does not have continuous production (to drive Rate is low) and other external factor, from the point of view of 11 monthly outputs in 2017 are 8676.98T/96% driving rate, convert 100% driving rate It should be 9353.20T, with improved average product 9147.13T/100%, two are closer to, and high yield is 2018 after improvement Year August is 9621.36T/100%, it is seen that before improving, complete equipment and technique are that there is no problem, are able to achieve the design output value 10WT/ is annual.
High list monthly output has 2.87% promotion, and factor among these should be the effect that acetylene purification and formaldehyde PH are adjusted.
Embodiment 2:
On the basis of embodiment 1, the present embodiment has also carried out related improvement to acetylene generator.
In acetylene generator long-play, the water of the carbide slag that system generates is easy blocking pipeline, and calcium carbide dust is easy stifled Wash cooling tower inner stuffing is filled in, causes separate unit generating system pressure difference higher, system resistance is larger, the production of separate unit generator load Ability decline.The acetylene of the present embodiment using the preparation of more acetylene generators, be respectively provided on every acetylene generator one with The displacement pipeline of ambient systems connection realizes that separate unit generator cuts out system and individually overhauls.Because ethynylation catalyst only has 2-3 months Service life, the replacement ethynylation catalyst that frequently stops production is needed when causing BDO production system, whole system is caused to run continuity It is poor, there are more acetylene generators in the system of the present embodiment, a displacement pipeline is set on every acetylene generator, is realized Separate unit generator cuts out system and individually overhauls.When a certain acetylene generator needs to overhaul, acetylene is sent out by displacement pipeline Raw device individually cuts out the maintenance of BDO production system, does not influence the continuous operation of BDO production system.
In actual use, separate unit acetylene generator cuts out system overhaul can add water and by forward and reverse water seal with forward and reverse water seal Exits and entrances valve is closed, and is completely cut off with other three generators, is not influenced its normal production work of excess-three platform generator thus.It is single Platform generator can be replaced by displacement pipeline from incineration torch.
Formaldehyde and acetylene prepare Isosorbide-5-Nitrae-butynediols in ethynylation device, and the operating pressure of ethynylation device is greater than 100 kpa.In common process, the pressure of ethynylation device is lower than 100 kpa, and the preferably kpa of 92 kpa ~ 98, the present embodiment exists Under the premise of formaldehyde pH value increases, acid solutions increase, the pressure in ethynylation device is turned up to 100 kpa or more, greatly Production efficiency is improved greatly, improves production capacity.After technique is applied in actual production after improvement, it is catalyzed from nearly two batches ethynylation The operating condition of agent sees that runing time and the BDO yield of single batch ethynylation catalyst are significantly improved.
It is preferred that being equipped with serpentine coil inside ethynylation device, there is for heating in ethynylation device flowing in the serpentine coil The high-temp liquid of chamber.The present embodiment is by the heat exchange of high-temp liquid, and the temperature control of ethynylation device inner cavity is 100 DEG C ~ 150 DEG C, ethynylation device inner cavity temperature is controlled under the premise of operating pressure is greater than 100 kpa, improves production capacity.
The pulp water sediment effect in acetylene generator is improved, the preparation purity and preparation quality of acetylene gas can be also improved. Therefore the present embodiment also needs to accomplish to improve pulp water effect of settling, reduces the cleaning frequency of acetylene generator.Ash wash slag water overflow Pipe guides washing slag water to dirt discharge groove, and washing slag water enters from the import of rapid pollution discharging slot upper end, and biggish particle is directly deposited to In cone, after 1 hour deposition, electromagnet is powered, and the permanent magnet on the magnetic field suction movable plate of generation drives movable plate It twitches, the particle of accumulation is quickly discharged under the pressure of water, powers off immediately to electromagnet, magnetic field is lost, in the drawing of tension spring Under power, mobile sheet reset is closed, and achievees the purpose that quick deslagging.
Embodiment 3:
On the basis of embodiment 1 and embodiment 2, the present embodiment has carried out de- ion waste water to shunt transformation, is sent respectively to dirt Water process, compound fertilizer factory and calcium carbide pour Slag treatment；System waste liquid is shunted, is integrated, by gasification and power digestion process.Reinforce Two dirty system process control, improve sewage load.Effect confirmation: system waste liquid, wastewater treatment can reach flat substantially Weighing apparatus, it is ensured that system long period heavy-duty service.
Pipeline is not replaced in acetylene generator totally 4 generators, original design individually, i.e., each system overhaul is by 4 The cleaning of platform generator complete overhaul, had not only increased maintenance workload but also had extended the repair time, had to the driving rate of system very big Influence, it is final to determine that process pipelines are transformed, increase the dedicated displacement pipeline autonomous Design pipeline arrangement of every generator Position, purchase material are voluntarily installed.For the effect of settling for improving acetylene pulp water, pulp water settling tank is increased, pulp water water after sedimentation Matter has certain effect, is further added by a settling tank.Effect confirmation: 1, effect after separate unit generator displacement dedicated pipeline puts into operation Preferably, cleaning workload when general overhaul is alleviated, the repair time is also shortened；2, pulp water settlement issues, which have, certain extenuates Gesture.
The series of detailed descriptions listed above only for feasible embodiment of the invention specifically Protection scope bright, that they are not intended to limit the invention, it is all without departing from equivalent implementations made by technical spirit of the present invention Or change should all be included in the protection scope of the present invention.
It is obvious to a person skilled in the art that invention is not limited to the details of the above exemplary embodiments, Er Qie In the case where without departing substantially from spirit or essential attributes of the invention, the present invention can be realized in other specific forms.Therefore, no matter From the point of view of which point, the present embodiments are to be considered as illustrative and not restrictive, and the scope of the present invention is by appended power Benefit requires rather than above description limits, it is intended that all by what is fallen within the meaning and scope of the equivalent elements of the claims Variation is included within the present invention.
In addition, it should be understood that although this specification is described in terms of embodiments, but not each embodiment is only wrapped Containing an independent technical solution, this description of the specification is merely for the sake of clarity, and those skilled in the art should It considers the specification as a whole, the technical solutions in the various embodiments may also be suitably combined, forms those skilled in the art The other embodiments being understood that.

Claims (7)

1. a kind of improvement technique for producing 1,4-butanediol, first uses acetylene and formaldehyde to prepare Isosorbide-5-Nitrae-butynediols for raw material, then Isosorbide-5-Nitrae-butynediols high-pressure hydrogenation is converted into 1,4-butanediol, which is characterized in that the pH value > 3.0 of the formaldehyde.
2. improvement technique according to claim 1, which is characterized in that it further includes acetylene that the acetylene reacts before with formaldehyde Acid pickling step, concentration >=85% of acid solution when the acetylene pickling.
3. improvement technique according to claim 2, which is characterized in that the concentration of the acid solution is greater than 89% ~ 93%.
4. improvement technique according to claim 1 or 2, which is characterized in that the acetylene uses more acetylene generator systems It is standby, the displacement pipeline being connected to ambient systems is respectively provided on every acetylene generator, realizing that separate unit generator is cut out is System individually maintenance.
5. improvement technique according to claim 1 or 2, which is characterized in that the formaldehyde and acetylene are in ethynylation device Isosorbide-5-Nitrae-butynediols is prepared, the operating pressure of the ethynylation device is greater than 100 kpa.
6. improvement technique according to claim 5, which is characterized in that serpentine coil is equipped with inside the ethynylation device, Flowing has the high-temp liquid for heating ethynylation device inner cavity in the serpentine coil.
7. improvement technique according to claim 1, which is characterized in that be converted into Isosorbide-5-Nitrae-fourth two in the Isosorbide-5-Nitrae-butynediols Hydrogenation catalyst is added during alcohol, the specific surface area of the hydrogenation catalyst is 60~130m2/ g, Kong Rongwei 0.35~ 0.6ml/g。
CN201910115957.3A 2019-02-15 2019-02-15 A kind of improvement technique producing 1,4-butanediol Pending CN109678660A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112457161A (en) * 2019-09-06 2021-03-09 南京延长反应技术研究院有限公司 Reinforcing system and process for preparing 1, 4-butanediol from acetylene and formaldehyde
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CN112457161A (en) * 2019-09-06 2021-03-09 南京延长反应技术研究院有限公司 Reinforcing system and process for preparing 1, 4-butanediol from acetylene and formaldehyde
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