阅读说明：本技术 一种海带漂烫液的资源化回收利用方法 (Method for recycling kelp blanching liquid ) 是由 谢全灵 洪专 于 2019-11-01 设计创作，主要内容包括：一种海带漂烫液的资源化回收利用方法,涉及盐渍海带。集成微滤澄清除杂工艺、柱层析脱除重金属工艺和纳米复合纳滤膜浓缩脱盐工艺,高效回收利用海带漂烫液的有效成分,制备得到纳滤浓缩液可作为海带调味品原料,同时纳滤透过液达到排放要求,消除了环境污染。采用模块化设计、工艺流程短、能耗低,可开发成集成式撬装设备,灵活可移动,特别适合海带漂烫加工生产季节性强的特点。所制备纳米复合纳滤浓缩液可在制备海带调味品原料中应用,其中砷含量小于0.5mg/kg。具有工艺流程简单高效、分离选择性高、能耗低、有效避免二次污染且易工业化放大等优点,特别适合低值资源再利用和消除环境污染的工业化生产。(A method for recycling kelp blanching liquid relates to salted kelp. The microfiltration clarification impurity removal process, the column chromatography heavy metal removal process and the nano composite nanofiltration membrane concentration desalination process are integrated, the effective components of the kelp blanching liquid are efficiently recycled, the prepared nanofiltration concentrated liquid can be used as a kelp seasoning raw material, and meanwhile, the nanofiltration permeate liquid meets the discharge requirement, so that the environmental pollution is eliminated. The method has the characteristics of modular design, short process flow, low energy consumption, flexible and movable development into integrated skid-mounted equipment, and strong seasonality, and is particularly suitable for the blanching processing production of kelp. The prepared nano composite nanofiltration concentrated solution can be applied to preparing kelp seasoning raw materials, wherein the arsenic content is less than 0.5 mg/kg. The method has the advantages of simple and efficient process flow, high separation selectivity, low energy consumption, effective avoidance of secondary pollution, easy industrial amplification and the like, and is particularly suitable for industrial production of recycling low-value resources and eliminating environmental pollution.)

1. A method for recycling kelp blanching liquid is characterized by comprising the following steps:

1) a microfiltration clarification impurity removal process;

2) a heavy metal removal process by column chromatography;

3) a concentration desalination process of a nano composite nanofiltration membrane.

2. The method for recycling the kelp blanching liquid as a resource according to claim 1, wherein in the step 1), the specific method of the microfiltration clarification impurity removal process comprises the following steps: adopting a tubular ceramic microfiltration membrane or a high-temperature resistant hollow fiber membrane to clarify and remove impurities from the kelp blanching liquid.

3. The method as claimed in claim 2, wherein the aperture of the microfiltration membrane is 0.1-1.4 μm.

4. The method for recycling the kelp blanching liquid as a resource according to claim 2, wherein the conditions of clarification and impurity removal are as follows: the operation temperature is 20-90 ℃, the operation pressure is 0.05-0.5 Mpa, the concentration multiple is 5-30 times, and the water addition multiple is 0.1-2.0 times.

5. The method for recycling the kelp blanching liquid as a resource according to claim 1, wherein in the step 2), the specific method of the column chromatography heavy metal removal process comprises the following steps: and removing heavy metals of arsenic, chromium and mercury in the microfiltration permeating liquid by adopting chelate resin column chromatography, and calculating by taking the volume of the chelate resin in the chromatographic column as 1BV, wherein the amount of the microfiltration permeating liquid on the column is 5-50 BV.

6. The method for recycling the kelp blanching liquid as a resource according to claim 1, wherein in the step 3), the specific method of the nano composite nanofiltration membrane concentration desalination process comprises the following steps: further concentrating and desalting the column chromatography effluent by using a nano-composite nanofiltration membrane to obtain a nano-composite nanofiltration concentrated solution.

7. The method as claimed in claim 6, wherein the selective separation layer of the nano composite nanofiltration membrane is a polyamide-carbon nanomaterial composite layer, and the carbon nanomaterial is at least one selected from graphene oxide, modified graphene oxide, graphene quantum dots, and modified graphene quantum dots.

8. The method for recycling the kelp blanching liquid as a resource according to claim 6, wherein the nano composite nanofiltration membrane has a molecular weight cut-off of 150-2000 Da.

9. The method for recycling the kelp blanching liquid as a resource according to claim 6, wherein the conditions of concentration and desalination are as follows: the operation temperature is 20-50 ℃, the operation pressure is 0.5-3 Mpa, and the concentration multiple is 5-30 times.

10. The method for recycling the kelp blanching liquid as a resource according to claim 6, wherein the prepared nano-composite nanofiltration concentrate is applied to preparing kelp seasoning raw materials, wherein the arsenic content is less than 0.5 mg/kg.

Technical Field

The invention relates to salted kelp, in particular to a resource recycling method of kelp blanching liquid, which integrates the technologies of microfiltration, chelating resin column chromatography, nano composite nanofiltration membrane and the like.

Background

The salted kelp is a kelp product which is prepared by taking fresh kelp as a raw material and processing the fresh kelp through the working procedures of boiling, cooling, salting, dehydrating, cutting and the like. At present, the annual output of the salted kelp in China exceeds 40 ten thousand tons, a large amount of blanching wastewater is generated in the process of producing the salted kelp, and detection shows that the blanching wastewater contains a plurality of active substances such as iodine, fucoidin, mannitol, alginic acid, fucoxanthin, iodine and the like. Meanwhile, the content of Suspended Solids (SS), COD and salt in the blanching wastewater is high, and if the wastewater is directly discharged without recycling and treatment, on one hand, environmental pollution is caused, and on the other hand, a large amount of various active ingredients with high activity and high added value contained in the blanching wastewater are lost, so that great resource waste is caused.

Chinese patent CN102992541B discloses a method for simultaneously extracting iodine and fucoidan from salted kelp blanching wastewater, which comprises the steps of adding caustic soda into denitrified kelp blanching wastewater to alkalize and flocculate fucoidan, floating and layering, filtering, and drying to obtain a crude product of fucoidan; pumping the kelp blanching wastewater without fucoidin into an acidification tank, adding an oxidant to completely oxidize iodine ions in the solution into iodine, and enriching the iodine by using ion exchange resin; with Na₂SO₃Desorbing iodine adsorbed in the resin by using the solution; by KClO₃Oxidizing the iodine ions in the desorption solution into iodine by using an oxidant, crystallizing, separating out, and centrifugally filtering to obtain crude iodine. The process adopted by the invention needs to add a large amount of caustic soda and acid, has high cost and low extraction efficiency, and can cause secondary environmental pollution.

Chinese patent CN104909339B discloses a method for preparing algae iodine by taking concentrated kelp blanching liquid as a raw material, which takes salted kelp blanching water as a raw material, and the concentrated liquid is obtained by heating and concentrating; treating the concentrated solution by a reverse osmosis device to obtain a treated solution; centrifuging the treatment solution to remove high-temperature precipitated salt, cooling to room temperature through a cooling tank, centrifuging to remove low-temperature salt, and preparing a semi-finished product solution; and processing the semi-finished product liquid to obtain the finished product of the seaweed iodine liquid. The invention introduces evaporation concentration, and has high energy consumption; and the reverse osmosis concentration process has large osmotic resistance because the salt can not be removed, and the reverse osmosis concentration can be operated only by needing ultrahigh pressure, so the energy consumption is also high.

The method aims at extracting one or two effective components, does not fully develop and utilize the rich active components in the kelp blanching water, and cannot effectively remove heavy metals and a large amount of sodium chloride in the kelp blanching water.

Disclosure of Invention

The invention aims to provide a method for recycling kelp blanching liquid, which is large-scale, clean and recyclable.

The invention comprises the following steps:

1) a microfiltration clarification impurity removal process;

in step 1), the specific method of the microfiltration clarification impurity removal process can be as follows: adopting a tubular ceramic microfiltration membrane or a high-temperature resistant hollow fiber membrane to clarify and remove impurities from the kelp blanching liquid; the aperture of the micro-filtration membrane can be 0.1-1.4 μm; the conditions for clarifying and impurity removing can be as follows: the operation temperature is 20-90 ℃, the operation pressure is 0.05-0.5 Mpa, the concentration multiple is 5-30 times, and the water addition multiple is 0.1-2.0 times;

2) a heavy metal removal process by column chromatography;

in step 2), the specific method of the column chromatography process for removing heavy metals may be: removing heavy metals such as arsenic, chromium, mercury and the like in the microfiltration permeating liquid by adopting chelate resin column chromatography, calculating according to the volume of the chelate resin in a chromatographic column as 1BV, and controlling the amount of the microfiltration permeating liquid on the column as 5-50 BV;

3) a concentration desalination process of a nano composite nanofiltration membrane.

In step 3), the specific method of the nano composite nanofiltration membrane concentration desalination process can be as follows: further concentrating and desalting the column chromatography effluent by using a nano-composite nanofiltration membrane to obtain a nano-composite nanofiltration concentrated solution; the selective separation layer of the nano composite nanofiltration membrane is made of a polyamide-carbon nano material composite layer, and the carbon nano material can be at least one of graphene oxide, modified graphene oxide, graphene quantum dots, modified graphene quantum dots and the like; the nano composite nanofiltration membrane has the molecular weight cutoff of 150-2000 Da; the concentration and desalination conditions may be: the operation temperature is 20-50 ℃, the operation pressure is 0.5-3 Mpa, and the concentration multiple is 5-30 times.

The nano composite nanofiltration concentrated solution prepared by the invention can be applied to preparing kelp seasoning raw materials, wherein the arsenic content is less than 0.5 mg/kg.

The invention integrates a microfiltration clarification impurity removal process, a column chromatography heavy metal removal process and a nano composite nanofiltration membrane concentration desalination process, efficiently recycles the effective components of the kelp blanching liquid, the prepared nanofiltration concentrated liquid can be used as a kelp seasoning raw material, and meanwhile, the nanofiltration permeate liquid meets the discharge requirement, thereby eliminating the environmental pollution. The invention adopts the modular design, has short process flow and low energy consumption, can be developed into integrated skid-mounted equipment, is flexible and movable, and is particularly suitable for the characteristics of strong seasonality of kelp blanching processing production.

The method has the advantages of simple and efficient process flow, high separation selectivity, low energy consumption, effective avoidance of secondary pollution, easy industrial amplification and the like, and is particularly suitable for industrial production for recycling low-value resources and eliminating environmental pollution.

Detailed Description

The following examples further illustrate the invention.

The embodiment of the invention comprises the following steps:

1) a microfiltration clarification impurity removal process: adopting a tubular ceramic microfiltration membrane or a high-temperature resistant hollow fiber membrane to clarify and remove impurities from the kelp blanching liquid; the aperture of the micro-filtration membrane can be 0.1-1.4 μm; the conditions for clarifying and impurity removing can be as follows: the operation temperature is 20-90 ℃, the operation pressure is 0.05-0.5 Mpa, the concentration multiple is 5-30 times, and the water addition multiple is 0.1-2.0 times;

2) the heavy metal removal process by column chromatography: removing heavy metals such as arsenic, chromium, mercury and the like in the microfiltration permeating liquid by adopting chelate resin column chromatography, calculating according to the volume of the chelate resin in a chromatographic column as 1BV, and controlling the amount of the microfiltration permeating liquid on the column as 5-50 BV;

3) the concentration and desalination process of the nano composite nanofiltration membrane comprises the following steps: further concentrating and desalting the column chromatography effluent by using a nano-composite nanofiltration membrane to obtain a nano-composite nanofiltration concentrated solution; the selective separation layer of the nano composite nanofiltration membrane is made of a polyamide-carbon nano material composite layer, and the carbon nano material can be at least one of graphene oxide, modified graphene oxide, graphene quantum dots, modified graphene quantum dots and the like; the nano composite nanofiltration membrane has the molecular weight cutoff of 150-2000 Da; the concentration and desalination conditions may be: the operation temperature is 20-50 ℃, the operation pressure is 0.5-3 Mpa, and the concentration multiple is 5-30 times.

Specific examples are given below.